Distribution of allophane and organic matter in podzol B horizons: reply to Buurman & Van Reeuwijk

The macromorphology, micromorphology and chemical nature of illuvial material in podzol B horizons and subsoils can be explained by contributions from two different migrating species: (a) a positively-charged mixed Al₂O₃-Fe₂O₃-SiO₂-H₂O sol incorporating minor amounts of adsorbed organic matter and silicate clay, and (b) negatively charged organic sols and solutions, carrying minor amounts of Al, Fe and clay. These species can also be generated within B horizons of high root activity. An alternative theory, that requires allophane to be formed in situ in the B horizon by microbial decomposition of precipitated organic complexes, fails to predict the observed distribution of allophane.     

Interference by organic complexation of Fe and A1 on the SO2-4 adsorption in Spodic B horizons in Sweden

The relations between pH, different fractions of Fe and A1 and Na₄P₂O₇-soluble C and the amount of adsorbed SO^2-₄ were assessed by analysing 63 soil samples from 14 podsolized soils in Sweden. The amount of adsorbed SO^2-₄ was significantly better correlated with the calculated amount of the inorganic fraction of Fe and A1 oxides obtained by subtracting Na₄P₂O₇-soluble Fe and A1 from oxalate-soluble Fe and Al than with the oxalate extraction alone. There was a close correlation between C and organically-bound S in the Na₄P₂O₇ extract which shows that the C:S ratio of the extracted fulvic acids is about constant in the soils studied. It was found that, as the proportion of organically-complexed Fe and Al increases, the ability of the soil to adsorb SO^2-₄ decreases. The amount of adsorbed SO^2-₄ expressed on the basis of the amounts of oxalate-soluble Fe and Al was generally smaller in areas with low S deposition (< 60 mmol m^-2 a^-1). The ratio between pyrophosphate-soluble C and oxalate-extractable Fe and Al was negatively correlated with pH in water. It was concluded that Fe and Al associated with organic matter cannot adsorb SO^2-₄ and that the degree of this association is pH dependent. These observations have important implications regarding the effects of anthropogenic acidification.     

The solubility characteristics of organic Al precipitates in allophanic Bs horizons could mimic those of Al hydroxides, and indicate the solubility of associated allophanes

It is shown that Al-humate and fulvate precipitates in Bs horizons of pH > 4.6 can be the source of the soluble aluminium which is rapidly released in equilibrium studies to give log₁₀{Al³⁺} + 3pH values near 9.4 at 8°C, so that it is not necessary to postulate an anomalously reactive but sparingly soluble Al(OH)₃ phase. These Al-organic precipitates will have reached equilibrium in the natural soil environment with the more slowly reacting hydroxy-aluminium precipitates present, including proto-imogolite allophane, but can release Al³⁺ much more rapidly than the inorganic precipitates in laboratory equilibrations and soil leaching episodes that yield lysimeter waters. Equilibrium concentrations of Al reported in a range of Bs horizons indicate that the allophanes present are less soluble than proto-imogolite sols prepared in the laboratory and matured for up to 2 years.     

Interactions of aluminium and fulvic acid in moderately acid solutions: stoichiometry of the H+/Al3+ exchange

Complexation with organic matter controls the activity of dissolved Al³⁺ in many soils. The buffering intensity of these soils is largely dependent on the H⁺/Al³⁺ exchange ratio, i.e. the number of protons consumed by the solid phase when one Al³⁺ is released. Here, the H⁺/Al³⁺ exchange ratio was determined from batch titrations using solutions of fulvic acid (FA) as a model for soil organic matter. Aluminium was added, from 1.04 to 6.29 mmol Al per g FA, which is within the range of humus‐bound Al found in the upper B horizon of podzolized soils. Furthermore, pH was varied with NaOH to give values between 3.5 and 5.0. The H⁺/Al³⁺ exchange ratio ranged between 1.49 and 2.23 with a mean of 1.94. It correlated positively with pH and the total concentration of Al present. Theoretically, this can be explained with a partial hydrolysis of bound Al. The slope of logAl (log₁₀ of Al³⁺ activity) against pH generally underestimated the actual exchange ratio, which can partly be attributed to the systems being diluted (100 mg FA l^?1). However, where 4 mmol Al or more had been added per g FA, the logAl slope gradually approached ?3 between pH 4.5 and 5.0. This might be the result of a shift from Al³⁺ activity control by humus complexation to control by Al(OH)₃(s).     

Determination of free Al3+ in soil solutions by capillary electrophoresis

Colorimetric and ion exchange methods are commonly used to distinguish and measure Al species in natural waters. Unfortunately they also include weakly complexed Al species in their ‘reactive' or ‘labile' Al fractions and thus are of limited value for the estimation of free Al³⁺. Capillary electrophoresis (CE) has the potential for direct measurement of Al³⁺, and its performance has been verified experimentally. The method also detected the stable and positively charged AlOx⁺ complex formed with oxalic acid. It was compared with a colorimetric and an ion exchange method by analysing artificial solutions containing low molecular weight organic acids as well as soil extracts and seepage waters and was found to be the only method closely matching the theoretically calculated values of free Al³⁺. In samples from the upper soil horizons of an acid forest soil less than 14% of total Al was present as free Al³⁺, whereas the colorimetric method found more than 65%, and the ion exchange method more than 80% of total Al in a ‘reactive' or ‘labile' form. The latter methods thus would seriously overestimate Al toxicity, whereas using CE Al toxicity is likely to be only slightly underestimated.     

PRECIPITATION OF AMORPHOUS ALUMINOSILICATES FROM SOLUTIONS CONTAINING MONOMERIC SILICA AND ALUMINIUM IONS

Monomeric silica solutions were mixed with solutions containing AlCl₃, or Al(OH)_2-55Cl_0-45 to give a SiO₂/Al₂O₃, ratio varying from 8 to 8.0 and were kept at pH 6–0, 7.0, or 8.0 over a period of about I year. All precipitates which formed from solutions with SiO₂/Al₂O₃ ratios of 1–0 or higher were X-ray amorphous. The SiO₂/Al₂O₂, ratio of the precipitate varied in the range from 1.0 to 3.0. It increased with the Si concentration and the SiO₂/Al₂O₃ ratio of the parent solution and with reaction time. The pH did not affect the SiO₂/Al₂O₃ ratio of the precipitate but did affect its dispersion and flocculation. Al³⁺ and Al(OH)_2.55^+0.45 reacted differently with silica and yielded different reaction products. These differences were interpreted in terms of the stability of hydroxy-Al polymer units in the reaction. The amount of NaOH per Al atom which was required to reach and maintain the same pH, increased with the increasing SiO₂/A1₂O ratio of the precipitate, but the value was generally lower than that predicted from ‘one in four’ substitution of Si by Al in four-fold co-ordination. A ‘neutralization’ of the positive charge on the hydroxy-Al cations by silica was pointed out also to be a cause of the extra acidity. Implications of these observations on synthetic amorphous aluminosilicates to the genesis, structure, and properties of their natural counterparts were discussed.     

Solubility characteristics of proto-imogolite sols: how silicic acid can de-toxify aluminium solutions

Proto-imogolite sols can be considered as highly dispersed forms of proto-imogolite allophane, the most widespread type of allophane in volcanic and non-volcanic soils world-wide. The solubility characteristics of such sols define the conditions of precipitation of allophanes in soils, and the maximum concentrations of aluminium released during acidic episodes from soils, such as podzols, that contain allophane. Direct measurement of Al, Si and pH values in equilibrium with proto-imogolite sols, approached from higher and lower pH, indicated a solubility equation: where log*K_so lay in the range 7.14 to 7.23 after equilibration for 4–24 weeks at 22 + 2°C in 17 of the 20 systems studied. The mean value of log *K_SO at 298 K was calculated as 7.02. This value indicates that proto-imogolite will be more stable than amorphous aluminium hydroxides at H₄SiO₄ concentrations above 5 × 10^?6m , but less stable than bayerite below 10^?3m H₄SiO₄, and than gibbsite below 10^?2m . Proto-imogolite is more stable than micro-crystalline gibbsite in 10^?4m H₄SiO₄, a typical minimum concentration in soil solutions and streams in landscapes where podzols are present. The rapid formation of proto-imogolite effectively prevents the formation of gibbsite seeds in soil, except in highly leached and warm environments, i.e. in older landscapes in the tropics. Although the presence of 10^?4m silicic acid has been found to eliminate the acute toxicity to fish exhibited by solutions containing 6–7 μm Al at pH 4.96, little or no proto-imogolite would form under these conditions. Silicic acid would, however, prevent the precipitation of aluminium hydroxides, and could inhibit the formation of the A1₁₃ polycation. These polymeric species are a likely cause of the increased toxicity exhibited by partially neutralized aluminium solutions.     

Aluminosilicate phases during initial clay formation: H+-Al3+–oxalic acid–silicic acid–Na+ system

The solid phases and the precipitation boundary characterizing the system H⁺-Al³⁺-oxalic acid-silicic acid-Na⁺ are discussed. Model experiments have been used to throw more light on two environmental problems: the formation of sparingly soluble aluminium silicates in oceans and alkaline lakes, which could be determining aluminium and silicate concentrations in pore waters of sediments, and the validity of inorganic and organic mechanisms of podzolization and their significance for soil science. pH and Tyndallometric measurements were performed at constant ionic strength of 0.6 M NaCl at 25°C. Three phases Al(OH)₄, H₄SiO₄ (phase Vi^a), Al₂, (OH)₆.H₄SiO₄ (phase VI^b) and NaAl(OH)₄.(H₄SiO₄), (phase VIII) determine the precipitation boundary. Phase NaAl(OH)₄.H₄SiO₄ (phase VII precipitates at 0.4pH units above NaAl(OH)₄.(H₄SiO₄)₂. Using a set of previously determined binary and ternary complexes, and phases of the subsystems, the following formation constants were deduced: Phases VI^a and VI^b are described as end-members of the allophane series with Si: Al ratios of 1:1 and 1.2. Phase VI^b was identified with protoimogolite allophane. These two phases are good model clays for podzolic soils and are extremely soluble at pH < 4. Sodium phases could be hydrous feldspathoids. These phases are possible in sediments of seawater or saline lakes. It is suggested that organic and inorganic mechanisms of podzolization operate sequentially and that neither of them alone can completely describe the process.     

Aluminium chemistry in two contrasted acid forest soils and headwater streams impacted by acid deposition,Vosges mountains,N.E. France

Al chemistry was studied in two acidic watersheds, one with a podzol, the other with an acid brown soil, in the Vosges mountains (N.E. France), by analysing both leaching and centrifugation soil solutions and spring waters over 3 yr. In the podzol, Al was mobilized in the eluvial horizons under the predominant influence of organic acidity, then leached down the profile as organic and F-bound Al. Strong undersaturation with respect to proto-imogolite and imogolite showed that the proto-imogolite theory of podzolization could not apply. Al was transferred from the soil to spring water mostly as Al³⁺ and Al-F. Al³⁺, as well as additional minor species (AlOH²⁺, AlSO₄ ⁺), originated from the redissolution of the top of the spodic horizons under the influence of both soil solution acidity and the occurrence of mobile anions derived from atmospheric deposition. Conversely, in the acid brown soil, Al mobilization was regulated by nitrate and occurred mainly as Al³⁺. Most of Al was retained in the deep soil and only traces of monomeric Al reached spring water. In the podzol eluvial horizons, soil solutions were undersaturated with respect to all relevant mineral phases and their chemical composition agree with the concept of a mobilization of Al from the solid soil organic Al and a control of Al³⁺ activity by complexation reaction with the solid and soluble soil organic matter and F. In the acid brown soil, soil solutions were found to be in equilibrium with natural alunite, and the formation of this mineral, if confirmed, would account for the occurrence of 'open' vermiculites instead of the expected hydroxy-Al interlayered vermiculites. Al solubility control in surface water of both watersheds remains unclear. The Al-F species in both watersheds and the likely control of Al solubility by alunite in the acid brown soil emphasize the influence of acid deposition on Al chemistry in acid watersheds.     

Inorganic sulphate extraction from SO2-impacted Andosols

Sulphate sorption on to the surface of short‐range ordered minerals and precipitation of Al‐hydroxy sulphate contribute to the acid neutralizing capacity of soils. The correct measurement of total inorganic sulphate is thus essential in soils that are accumulating SO₄^2– anions. We extracted SO₄^2– by various solutions, namely 0.005 m Ca(NO₃)₂, 0.016 m KH₂PO₄, 0.5 m NH₄F and 0.2 m acidic NH₄‐oxalate (pH 3), from Vitric and Eutric Andosols exposed to prolonged deposition of acid and SO₂ from an active volcano (Masaya, Nicaragua). We attributed sulphate extractable by KH₂PO₄ (20–3030 mg kg^?1) to anion‐exchangeable SO₄^2–, which was much smaller than NH₄F‐ and oxalate‐extractable SO₄^2– (400–9680 and 410–10 480 mg kg^?1, respectively). Our results suggest the occurrence of a sparingly soluble Al‐hydroxy‐mineral phase extractable by both NH₄F and oxalate. The formation of Al‐hydroxy minerals would result from the combination of enhanced weathering caused by strong acid loading and simultaneous occurrence of large SO₄^2– concentrations in soil solution. Oxalate extracted slightly more inorganic SO₄^2– than did NH₄F, this additional amount of SO₄^2– correlating strongly with oxalate‐extractable Si and Fe contents. Preferential occlusion of SO₄^2– by short‐range ordered minerals, especially ferrihydrite, explains this behaviour. If we exclude the contribution of occluded sulphate then oxalate and NH₄F mobilize similar amounts of SO₄^2– and are believed to mobilize all of the inorganic SO₄^2– pool.     

Estimating diesel degradation rates from N2, O2 and CO2 concentration versus depth data in a loamy sand

The degradation rate of the pollutant is often an important parameter for designing and maintaining an active treatment system or for determining the rate of natural attenuation. A quasi‐steady‐state gas transport model based on Fick’s law with a correction term for advective flux, for estimating diesel degradation rates from N₂, O₂ and CO₂ concentration versus depth data, was evaluated in a laboratory column study. A loamy sand was spiked with diesel fuel at 0, 1000, 5000 and 10 000 mg kg⁻¹ soil (dry weight basis) and incubated for 15 weeks. Soil gas was sampled weekly at 6 selected depths in the columns and analysed for O₂, CO₂ and N₂ concentrations. The agreement between the measured and the modelled concentrations was good for the untreated soil (R²= 0.60) and very good for the soil spiked with 1000 mg kg⁻¹ (R²= 0.96) and 5000 mg kg⁻¹ (R²= 0.97). Oxygen consumption ranged from −0.15 to −2.25 mol O₂ m⁻³ soil day⁻¹ and CO₂ production ranged from 0.20 to 2.07 mol CO₂ m⁻³ soil day⁻¹. A significantly greater mean O₂ consumption (P < 0.001) and CO₂ production (P < 0.005) over time was observed for the soils spiked with diesel compared with the untreated soil, which suggests biodegradation of the diesel substrate. Diesel degradation rates calculated from respiration data were 1.5–2.1 times less than the change in total petroleum hydrocarbon content. The inability of this study to correlate respiration data to actual changes in diesel concentration could be explained by volatilization, long‐term sorption of diesel hydrocarbons to organic matter and incorporation of diesel hydrocarbons into microbial biomass, aspects of which require further investigation.     

铁铝氢氧化物对两种土壤和高岭石表面K+和NH4+解吸的影响

Potassium (K) and nitrogen (N) are essential nutrients for plants. Adsorption and desorption in soils affect K+ and NH + 4 availabilities to plants and can be affected by the interaction between the electrical double layers on oppositely charged particles because the interaction can decrease the surface charge density of the particles by neutralization of positive and negative charges. We studied the effect of iron (Fe)/aluminum (Al) hydroxides on desorption of K+ and NH + 4 from soils and kaolinite and proposed desorption mechanisms based on the overlapping of diffuse layers between negatively charged soils and mineral particles and the positively charged Fe/Al hydroxide particles. Our results indicated that the overlapping of diffuse layers of electrical double layers between positively charged Fe/Al hydroxides, as amorphous Al(OH) 3 or Fe(OH) 3 , and negatively charged surfaces from an Ultisol, an Alfisol, and a kaolinite standard caused the effective negative surface charge density on the soils and kaolinite to become less negative. Thus the adsorption affinity of these negatively charged surfaces for K+ and NH + 4 declined as a result of the incorporation of the Fe/Al hydroxides. Consequently, the release of exchangeable K+ and NH +4 from the surfaces of the soils and kaolinite increased with the amount of the Fe/Al hydroxides added. The greater the positive charge on the surfaces of Fe/Al hydroxides, the stronger was the interactive effect between the hydroxides and soils or kaolinite, and thus the more release of K+ and NH + 4 . A decrease in pH led to increased positive surface charge on the Fe/Al hydroxides and enhanced interactive effects between the hydroxides and soils/kaolinite. As a result, more K+ and NH + 4 were desorbed from the soils and kaolinite. This study suggests that the interaction between oppositely charged particles of variable charge soils can enhance the mobility of K+ and NH + 4 in the soils and thus increase their leaching loss.     

SYNTHETIC ALLOPHANE AND IMOGOLITE

In order to prepare allophane and imogolite in the laboratory, solutions containing l–2× 10^–3 M orthosilicic acid and 4–0.5 × 10^–3 M A1C1₃ (SiO₂/Al₂O₃ molar ratio; 0.5, 1.0, 2.0, 4.0 and 8.0) were heated at 95–100°C for 113 hours after addition of NaOH (NaOH/Al molar ratio; 1.0, 2.0, 2.8 and 3.0). Boehmite was found in the precipitates from all solutions with initial SiO₂/Al₂O₃ ratios of 0.5. Imogolite was found with allophane II in the products from solutions with SiO₂/Al₂O₃ ratios of 1.0 or greater and with NaOH/Al ratios of 2.8 or less (final pH 5.0), whereas allophane I was found in the precipitates from solutions with the same SiO₂/Al₂O₃ ratios but with the NaOH/Al ratio of 3.0 (final pH = 5.0–6.3). The mode of formation, chemical composition, infrared spectra, electron micrographs, electron diffraction patterns and differential thermal analysis curves of synthetic imogolite and allophanes (I and II) were compared with those of their natural counterparts.     

pH and solubility of aluminium in acidic forest soils: a consequence of reactions between organic acidity and aluminium alkalinity

Data from two Podzol O and E horizons, sampled in 1-cm layers at 13 points within 2 m × 2 m plots, were used to test the hypothesis that the composition of hydrogen ions (H) and aluminium (Al) adsorbed to the solid-phase soil organic matter (SOM) determines pH and Al solubility in organic-rich acidic forest soils. Organically adsorbed Al was extracted sequentially with 0.5 m CuCl₂ and organically adsorbed H was determined as the difference between total acidity titrated to pH 8.2 and Al extracted in 0.5 m CuCl₂. The quotient between fractions of SOM sites binding Al and H (N_Al/N_H) is shown to determine the variation in pH and Al solubility. It is furthermore shown that models in which pH and Al solubility are linked via a pH-dependent solubility of an Al hydroxide and in which cation exchange between Al³⁺ and Ca²⁺, rather than cation exchange between Al³⁺ and H⁺, is the main pH-buffering process cannot be used to simulate pH or Al solubility in O and E horizons. The fraction of SOM sites adsorbing Al increased by depth in the lower O and throughout the E horizon at the same magnitude as sites adsorbing H decreased. The fraction of sites binding the cations Ca²⁺ + Mg²⁺ + K⁺ + Na⁺ remained constant. It is suggested that a net reaction between Al silicates (proton acceptors) and protonated functional groups in SOM (proton donors) is the long-term chemical process determining the composition of organically adsorbed H and Al in the lower part of the O and in the E horizon of Podzols. Thus, in the long term, pH and Al solubility are determined by the interaction between organic acidity and Al alkalinity.     

SOIL ALKALINITY. II THE EFFECTS OF Na2CO3 ON IRON AND MANGANESE SUPPLY TO TOMATOES

Sodium carbonate added to nutrient solution in sand culture depressed the growth of tomatoes both by the influence of high pH and HCO₃^? causing chlorosis and by the effect of Na⁺. Foliar sprays of iron and manganese removed chlorosis and increased growth but did not remove the effect of Na. In a sandy soil Na₂CO₃ did not cause chlorosis but Na⁺ depressed yield. Chelated Fe and Mn in the soil solutions (up to 7.3 × 10^?4 M Fe and 2.6 × 10^?5 M Mn at pH 9.0) were sufficient to supply the crop needs as shown by a second sand culture experiment where plants were fed with nutrient solution plus extracted soil solution.     

Dynamics of aqueous aluminum species in a podzol affected by experimental MgSO4 and (NH4)2SO4 treatments

Chemistry of aqueous Al in a podzol on a Norway spruce (Picea abies [L.] Karst.) site in the Black Forest (SW Germany) and changes induced by experimental applications of MgSO₄ were studied. Soil solution taken from the O, E and BC horizons were analyzed for the fractions ‘labile monomeric Al’, ‘non-labile monomeric Al’, and ‘acid-reactive Al’. The activities of ‘inorganic monomeric Al’ species and the saturation indices (SI) of the soil solution with respect to Al-bearing minerals were calculated using the equilibrium speciation model WATEQF. On the untreated plot, soil leachates are characterized by Al_tot concentrations of 0.1 mg L^?1 (mineral soil). In the O horizon, the fractions ‘acidsoluble Al’ and ‘non-labile monomeric Al’ (mainly organically complexed Al) together comprise 80% of Al_tot. In the leachates from the mineral soil Al³⁺ prevails, being 50% of Al_tot. Al-F-complexes make up 5 to 10% in all horizons. MgSO₄ and (NH₄)₂SO₄ treatments resulted in an intense Al mobilization up to 50 mg L^?1. In this situation, 60% of Al_tot is covered by Al³⁺ and 40% by non-phytotoxic Al-SO₄-complexes. After rainfall events, mobilized Al is quickly translocated into the subsoil, with water flow through macropores then appearing to be an important mechanism. In both treatments, soil solution chemistry was favorable for the precipitation of the Al(OH)SO₄-type minerals alunite and jurbanite. However, a control of Al solubility by this process is not likely due to kinetic restraints. Application of MgSO₄ was followed by an increase of the Mg/Al molar ratio in the soil solution, whereas the Ca/Al ratio decreased. After treatment with (NH₄)₂SO₄ both the Ca/Al and the Mg/Al ratios deteriorated.     

Nitrous oxide production by nitrification and denitrification in soil aggregates as affected by O2 concentration

Nitrous oxide emitted by soils can be produced either by denitrification in anoxic conditions or by nitrification in presence of O₂. The relative importance of the two processes, particularly under varied partial pressures of O₂, is not always known. This paper focuses on the influence of O₂ concentration on N₂O production by nitrification and denitrification in an arable Orthic Luvisol. Soil aggregates (2-3 mm size), water unsaturated, received 116 mg N kg⁻¹ as ammonium sulphate labelled with ¹⁵N and were incubated during 14 days at different O₂ partial pressures: 0, 0.35, 0.76, 1.5, 4.3 and 20.4 kPa. A ¹⁵N tracing technique was used to quantify nitrification and denitrification rates. ¹⁵N₂O and ¹⁵N₂ were measured. Oxygen pressure appeared to strongly influence both nitrification and denitrification rates and also N₂O emissions. Nitrification rates were reduced by a factor of 6-9 when O₂ decreased from 20.4 to 0.35 kPa. They were highly correlated with O₂ consumption rates. Denitrification mainly occurred in complete anoxic conditions. The proportion of N₂O emitted by denitrification was estimated by two independent methods: one based on ¹⁵N tracing using isotope composition of NH₄, NO₃ and N₂O, the other based on the measurement of the ¹⁵N₂O:¹⁵N₂ ratio. The two methods gave close results. The highest N₂O emissions were obtained under complete anoxic conditions and were due to denitrification. However, N₂O emissions almost as important were obtained at day 14 with 1.5 kPa O₂ pressure, and they were due to nitrification. Nitrification was the main source of N₂O at O₂ concentrations greater than 0.35 kPa. The amounts of N₂O-N emitted by nitrification were linearly related to the amounts of N nitrified, but the slope of the regression was highly dependent on O₂ concentration: it varied from 0.16 to 1.48% when O₂ concentration was reduced from 20.4 to 0.76 kPa. Emissions of N₂O by nitrification may then be quite significant if nitrification occurs at a reduced O₂ concentration.     

Measuring N2O emissions from organic soils by closed chamber or soil/snow N2O gradient methods

Drained organic soils contribute substantial amounts of nitrous oxide to the global atmosphere, and we should be able to estimate this contribution. We have investigated when the fluxes of N₂O from drained forested or cultivated organic soils could be determined by calculating the fluxes from the concentration gradients of the gas in soil or snow according to Fick's law of diffusion. A static chamber method was applied as a control technique for the gas gradient method. Concentrations of N₂O in soil varied from 296 nl l^?1 to 8534 nl l^?1 during the snow‐free periods and were greatest in the early summer. Our results suggest that the gas gradient method can be used to estimate N₂O emissions from drained organic soils. There was some systematic difference in the N₂O fluxes measured with these two methods, which we attributed to the differences in weather between years 1996 and 1997. In the wet summer of 1996 the chamber method gave greater flux rates than the gas gradient method, and the reverse was true in the dry summer of 1997. In the forest the N₂O fluxes measured with the two methods agreed well. The gas gradient is convenient and fast for measuring N₂O emissions from fairly dry organic unfrozen soil. In winter the diffusion calculation based on the N₂O gradients in snow and the chamber method gave fairly similar flux rates and provided adequate estimates of the fluxes of N₂O in winter.     

Changes in forest soil organic matter pools after a decade of elevated CO2 and O3

The impact of rising atmospheric carbon dioxide (CO₂) may be mitigated, in part, by enhanced rates of net primary production and greater C storage in plant biomass and soil organic matter (SOM). However, C sequestration in forest soils may be offset by other environmental changes such as increasing tropospheric ozone (O₃) or vary based on species-specific growth responses to elevated CO₂. To understand how projected increases in atmospheric CO₂ and O₃ alter SOM formation, we used physical fractionation to characterize soil C and N at the Rhinelander Free Air CO₂-O₃ Enrichment (FACE) experiment. Tracer amounts of ¹⁵NH₄⁺ were applied to the forest floor of Populus tremuloides, P. tremuloides-Betula papyrifera and P. tremuloides-Acer saccharum communities exposed to factorial CO₂ and O₃ treatments. The ¹⁵N tracer and strongly depleted ¹³C-CO₂ were traced into SOM fractions over four years. Over time, C and N increased in coarse particulate organic matter (cPOM) and decreased in mineral-associated organic matter (MAOM) under elevated CO₂ relative to ambient CO₂. As main effects, neither CO₂ nor O₃ significantly altered ¹⁵N recovery in SOM. Elevated CO₂ significantly increased new C in all SOM fractions, and significantly decreased old C in fine POM (fPOM) and MAOM over the duration of our study. Overall, our observations indicate that elevated CO₂ has altered SOM cycling at this site to favor C and N accumulation in less stable pools, with more rapid turnover. Elevated O₃ had the opposite effect, significantly reducing cPOM N by 15% and significantly increasing the C:N ratio by 7%. Our results demonstrate that CO₂ can enhance SOM turnover, potentially limiting long-term C sequestration in terrestrial ecosystems; plant community composition is an important determinant of the magnitude of this response.     

Investigation of soils developed on volcanic materials in Nisyros Island, Greece

Soils that are forming on volcanic parent materials have unique physical and chemical properties and in most cases, on wet and humid climates, are classified as Andisols. The main purpose of this study is to examine if the soils that are forming on volcanic materials under a dry Mediterranean climate, in Nisyros Island (Greece), meet the requirements to be classified as Andisols. Soils from seven sites were sampled and examined for their main physico-chemical properties and selective dissolution analysis. Dithionite–citrate–bicarbonate (DCB) extractable Al and Fe (Ál_d, Fe_d), acid ammonium oxalate extractable Al, Fe, and Si (Ál_o, Fe_o and Si_o), and sodium pyrophosphate extractable Al and Fe (Al_p, Fe_p) were measured. In addition, Al and Si were determined after reaction with hot 0.5 M NaOH, (Al_NaOH and Si_NaOH) and with Tiron-(C₆H₄Na₂O₈S₂), (Al_T and Si_T). P-retention was also measured. The soils are characterised by coarse texture, low organic matter content, low values of cation exchange capacity (CEC), and high pH values. Values of Si_o, Al_o and Fe_o are less than 0.022%, 0.09% and 0.35% respectively, highlighting the lack of noncrystalline components. The ratio (Fe_d–Fe_o)100/Fe_d is quite high expressing the degree of crystallisation of free iron oxides. For all samples tested, values of the Al_o + 1/2Fe_o index are extremely low (< 0.24%). High Si_NaOH and Si_T (arising 2.76% and 2.18% respectively) indicate the presence of silica in amorphous forms. P-retention values are very low (< 12.6%). The results indicated the absence of noncrystalline minerals except for amorphous silica, and do not exhibit andic or vitric soil characteristics to be classified as Andisols.