Effect of temperature and rhizosphere processes on pedogenic carbonate recrystallization: Relevance for paleoenvironmental applications

In soils of arid and semiarid climates, dissolution of primary (lithogenic) carbonate and recrystallization with CO₂ from soil air leads to precipitation of pedogenic carbonates and formation of calcic horizons. Thus, their carbon isotope composition represents the conditions prevailing during their formation. However, the widespread use of the isotopic signature (δ¹³C, δ¹⁸O, Δ¹⁴C) of pedogenic carbonates for reconstruction of local paleovegetation, paleoprecipitation and other environmental conditions lacks knowledge of the time frame of pedogenic carbonate formation, which depends on climatic factors. We hypothesized that temperature-dependent biotic processes like plant growth and root and rhizomicrobial respiration have stronger influence on soil CaCO₃ recrystallization than abiotic temperature-dependent solubility of CO₂ and CaCO₃.To assess the effect of temperature on initial CaCO₃ recrystallization rates, loess with primary CaCO₃ was exposed to ¹⁴CO₂ from root and rhizomicrobial respiration of plants labeled in ¹⁴CO₂ atmosphere at 10, 20 or 30 °C. ¹⁴C recovered in recrystallized CaCO₃ was quantified to calculate amounts of secondary CaCO₃ and corresponding recrystallization rates, which were in the range of 10⁻⁶-10⁻⁴ day⁻¹, meaning that 10⁻⁴-10⁻²% of total loess CaCO₃ were recrystallized per day. Increasing rates with increasing temperature showed the major role of biological activities like enhanced water uptake by roots and respiration. The abiotic effect of lower solubility of CO₂ in water by increasing temperature was completely overcompensated by biotic processes. Based on initial recrystallization rates, periods necessary for complete recrystallization were estimated for different temperatures, presuming that CaCO₃ recrystallization in soil takes place mainly during the growing season. Taking into account the shortening effect of increasing temperature on the length of growing season, the contrast between low and high temperature was diminished, yielding recrystallization periods of 5740 years, 4330 years and 1060 years at 10, 20 and 30 °C, respectively. In summary, increasing CaCO₃ recrystallization rates with increasing temperature demonstrated the important role of vegetation for pedogenic CaCO₃ formation and the predominantly biotic effects of growing season temperature.Considering the long periods of pedogenic carbonate formation lasting to some millennia, we conclude that methodological resolution of paleoenvironmental studies based on isotope composition of pedogenic carbonates is limited not by instrumental precision but by the time frame of pedogenic carbonate formation and hence cannot be better than thousands of years.     

The origin of carbonates in termite mounds of the Lubumbashi area, D.R. Congo

The origin of carbonate accumulations in termite mounds is a controversial issue. This study is an attempt to elucidate the processes of carbonate precipitation in Macrotermes mounds built on Ferralsols in Upper Katanga, D.R. Congo, whereby a differentiation between pedogenic and inherited carbonates is considered. Carbonate features were investigated for a 9 m deep termite-mound profile, and for an 18 m wide cross-section through a termite mound and the adjacent soil, using field and laboratory techniques. Field evidence for a pedogenic origin includes morphological type (soft powdery materials, nodules, and coatings on ped surfaces) and distribution patterns of the carbonates. Thin-section studies reveal that the carbonates occur predominantly as impregnative orthic nodules and less commonly as coatings, both clearly pedogenic; calcareous pellets are interpreted as locally reworked pedogenic carbonates. X-ray diffraction (XRD), scanning electron microscopy/energy dispersive X-ray spectrometry (SEM-EDS) and stable isotope (δ¹³C) analyses show that all isolated carbonate features consist of high-Mg calcite (4.9-12.3 mol% MgCO₃) with δ¹³C signatures ranging from − 13.2‰ to − 11.5‰. Weddellite (CaC₂O₄. 2H₂O) is identified in a thin-section and by XRD analysis, and appears to be locally transformed into calcite. The stable isotope composition of carbon suggests that calcite precipitated in equilibrium with soil CO₂ generated during decomposition of soil organic matter, and locally most likely during oxidation of oxalate. This study proves that carbonates which accumulated in Macrotermes mounds are pedogenic precipitates, whose deposition is partly related to microbial decay of organic matter, subsequently redistributed to some extent by abiotic dissolution-reprecipitation and termite activity.     

The stable carbon isotope composition of soil organic carbon and pedogenic carbonates along a bioclimatic gradient in the Palouse region,Washington State,USA

Isotopic signatures of soil components are commonly used to infer past ecologic and climatic shifts in the soil record. The theory behind the fractionation of isotopes that occurs during ecosystem processes is well understood; however, few isotopic studies have explored ecosystem relationships in modern soils. We discuss relationships of stable carbon isotopic signatures in plant tissue, soil organic carbon (SOC), laboratory-respired CO₂, and modern carbonates at 10 sites (seven containing pedogenic carbonates) along a C₃-dominated climatic gradient (mean annual precipitation (MAP) ranging from 200 to 1000 mm) in the Palouse region of eastern Washington state.A horizon soil organic carbon (SOC) δ¹³C values varied from −24.3‰ to −25.9‰ PDB. Values in the arid portion of the gradient (200 to approximately 500 mm MAP) generally decreased and linear regression of SOM ¹³C vs. MAP was significant (r²=0.71, p=0.02). Trends in plant-¹³C of two grass species (Agropyron spicatum and Festuca idahoensis) found throughout this portion of the gradient were similar to that of SOC. Mean pedogenic carbonate δ¹³C values varied from −4.1‰ to −10.8‰ PDB. Linear regression was significant for carbonate ¹³C vs. MAP (r²=0.79, p=0.007), estimated above-ground productivity (r²=0.88, p=0.002) and soil carbon content (r²=0.83, p=0.004). Carbonate δ¹³C values at the most arid site exhibited higher variability than other sites (presumably due to greater spatial variation in plant respiration vs. atmospheric diffusion). Our data suggest that carbon isotopic relationships among ecosystem components may prove useful in determining ecosystem level properties in modern systems, and potentially in ancient systems as well.     

Submicroscopy and stable isotope geochemistry of carbonates and associated palygorskite in Iranian Aridisols

Pedogenic carbonates in arid and semi-arid regions of the world have a great significance as palaeoecological and palaeoclimatological indicators and form a major pool in the carbon cycle. We analysed the ultra-microfabric and the stable isotope composition of C and O in pedogenic carbonates in colluvial soils derived from limestone in an arid region of central Iran. Our objective was to determine the conditions for the formation of soft pedogenic carbonate nodules and their co-existence with palygorskite in the palaeo-argillic horizon. Scanning electron microscopy revealed that the calcite aggregates were matted with palygorskite. Ultra-microtome cuts, examined using transmission electron microscopy, provided more detailed information about the fundamental particle association of secondary carbonates and palygorskite. Although less abundant, other silicate clays were detected in both the acid-insoluble clay fractions and in ultra-cuts, mostly in fine clay size, suggesting the engulfing of palygorskite by growing calcite or illuviation of palygorskite during or after formation of the calcite. Coatings of illuvial clays on calcite crystals support the hypothesis that palygorskite was trapped by pedogenic carbonate when the climate was wetter than it is today to form an argillic horizon. However, electron microscopic evidence of the occurrence of fibres on the immediate pedogenic carbonate particle surfaces suggests the in situ formation of palygorskite. The δ¹³C and δ¹⁸O values of pedogenic carbonates suggest that these carbonates were formed in an environment with more available moisture and more C4 plants than now.     

Carbon and nitrogen mineralization in acidic, limed and calcareous agricultural soils: Apparent and actual effects

Soil pH and calcium carbonate contents are often hypothesized to be important factors controlling organic matter turnover in agricultural soils. The aim of this study was to differentiate the effects of soil pH from those related to carbonate equilibrium on C and N dynamics. The relative contributions of organic and inorganic carbon in the CO₂ produced during laboratory incubations were assessed. Five agricultural soils were compared: calcareous (74% CaCO₃), loess (0.2% CaCO₃) and an acidic soil which had received different rates of lime 20 years ago (0, 18 or 50 t ha⁻¹). Soil aggregates were incubated with or without rape residues under aerobic conditions for 91 days at 15 °C. The C and N mineralized, soil pH, O₂ consumption and respiratory quotient (RQ=ΔCO₂/ΔO₂) were monitored, as well as the δ¹³C composition of the evolved CO₂ to determine its origin (mineral or organic). Results showed that in non-amended soils, the cumulative CO₂ produced was significantly greater in the limed soil with a pH>7 than in the same soil with less or no lime added, whereas there was no difference in N mineralization or in O₂ consumption kinetics. We found an exponential relationship between RQ values and soil pH, suggesting an excess production of CO₂ in alkaline soils. This CO₂ excess was not related to changes in substrate utilization by the microbial biomass but rather to carbonates equilibrium. The δ¹³C signatures confirmed that the CO₂ produced in soils with pH>7 originated from both organic and mineral sources. The contribution of soil carbonates to CO₂ production led to an overestimation of organic C mineralization (up to 35%), the extent of which depended on the nature of soil carbonates but not on the amount. The actual C mineralization (derived from organic C) was similar in limed and unlimed soil. The amount of C mineralized in the residue-amended soils was ten times greater than in the basal soil, thus masking the soil carbonate contribution. Residue decomposition resulted in a significant increase in soil pH in all soils. This increase is attributed to the alkalinity and/or decarboxylation of organic anions in the plant residue and/or to the immobilization of nitrate by the microbial biomass and the corresponding release of hydroxyl ions. A theoretical composition (C, O, H, N) of residue and soil organic matter is proposed to explain the RQ measured. It emphasizes the need to take microbial biomass metabolism, O₂ consumption due to nitrification and carbon assimilation yield into account when interpreting RQ data.     

Black carbon decomposition and incorporation into soil microbial biomass estimated by C labeling

Incomplete combustion of organics such as vegetation or fossil fuel led to accumulation of charred products in the upper soil horizon. Such charred products, frequently called pyrogenic carbon or black carbon (BC), may act as an important long-term carbon (C) sink because its microbial decomposition and chemical transformation is probably very slow. Direct estimations of BC decomposition rates are absent because the BC content changes are too small for any relevant experimental period. Estimations based on CO₂ efflux are also unsuitable because the contribution of BC to CO₂ is too small compared to soil organic matter (SOM) and other sources.We produced BC by charring ¹⁴C labeled residues of perennial ryegrass (Lolium perenne). We then incubated this ¹⁴C labeled BC in Ah of a Haplic Luvisol soil originated from loess or in loess for 3.2 years. The decomposition rates of BC were estimated based on ¹⁴CO₂ sampled 44 times during the 3.2 years incubation period (1181 days). Additionally we introduced five repeated treatments with either 1) addition of glucose as an energy source for microorganisms to initiate cometabolic BC decomposition or 2) intensive mixing of the soil to check the effect of mechanical disturbance of aggregates on BC decomposition. Black carbon addition amounting to 20% of C_org of the soil or 200% of C_org of loess did not change total CO₂ efflux from the soil and slightly decreased it from the loess. This shows a very low BC contribution to recent CO₂ fluxes. The decomposition rates of BC calculated based on ¹⁴C in CO₂ were similar in soil and in loess and amounted to 1.36 10⁻⁵ d⁻¹ (=1.36 10⁻³% d⁻¹). This corresponds to a decomposition of about 0.5% BC per year under optimal conditions. Considering about 10 times slower decomposition of BC under natural conditions, the mean residence time (MRT) of BC is about 2000 years, and the half-life is about 1400 years. Considering the short duration of the incubation and the typical decreasing decomposition rates with time, we conclude that the MRT of BC in soils is in the range of millennia.The strong increase in BC decomposition rates (up to 6 times) after adding glucose and the decrease of this stimulation after 2 weeks in the soil (and after 3 months in loess) allowed us to conclude cometabolic BC decomposition. This was supported by higher stimulation of BC decomposition by glucose addition compared to mechanical disturbance as well as higher glucose effects in loess compared to the soil. The effect of mechanical disturbance was over within 2 weeks. The incorporation of BC into microorganisms (fumigation/extraction) after 624 days of incubation amounted to 2.6 and 1.5% of ¹⁴C input into soil and loess, respectively. The amount of BC in dissolved organic carbon (DOC) was below the detection limit (<0.01%) showing no BC decomposition products in water leached from the soil.We conclude that applying ¹⁴C labeled BC opens new ways for very sensitive tracing of BC transformation products in released CO₂, microbial biomass, DOC, and SOM pools with various properties.     

Stem labeling results in different patterns of 14C rhizorespiration and 15N distribution in plants compared to natural assimilation pathways

To investigate C and N rhizodeposition, plants can be ¹³C‐¹⁵N double‐labeled with glucose and urea using a stem‐feeding method (wick method). However, it is unclear how the ¹³C applied as glucose is released into the soil as rhizorespiration in comparison with the ¹³C applied as CO₂ using a natural uptake pathway. In the present study, we therefore compared the short‐term fate of ¹⁴C and ¹⁵N in white lupine and pea plants applied either by the wick method or the natural pathways of C and N assimilation. Plants were pulse‐labeled in ¹⁴CO₂‐enriched atmosphere and ¹⁵N urea was applied to the roots (atmosphere–soil) following the natural assimilation pathways, or plants were simultaneously labeled with ¹⁴C and ¹⁵N by applying a ¹⁴C glucose–¹⁵N urea solution into the stem using the wick method. Plant development, soil microbial biomass, total rhizorespiration, and distribution of N in plants were not affected by the labeling method used but by plant species. However, the ¹⁵N : N ratio in plant parts was significantly (p < 0.05) affected by the labeling method, indicating more homogeneous ¹⁵N enrichment of plants labeled via root uptake. After ¹⁴CO₂ atmosphere labeling of plants, the cumulated ¹⁴CO₂ release from roots and soil showed the common saturation dynamics. In contrast, after ¹⁴C‐glucose labeling by the wick method, the cumulated ¹⁴CO₂ release increased linearly. These results show that ¹⁴C applied as glucose using the wick method is not rapidly transferred to the roots as compared to a short‐term ¹⁴CO₂ pulse. This is partly due to a slower ¹⁴C uptake and partly due to slow distribution within the plant. Consequently, ¹⁴C‐glucose application by the wick method is no pulse‐labeling approach. However, the advantages of the wick method for ¹³C‐¹⁵N double labeling for estimating rhizodeposition especially under field conditions requires further methodological research.     

Three‐source partitioning of CO2 efflux from maize field soil by 13C natural abundance

A natural‐¹³C‐labeling approach—formerly observed under controlled conditions—was tested in the field to partition total soil CO₂ efflux into root respiration, rhizomicrobial respiration, and soil organic matter (SOM) decomposition. Different results were expected in the field due to different climate, site, and microbial properties in contrast to the laboratory. Within this isotopic method, maize was planted on soil with C₃‐vegetation history and the total CO₂ efflux from soil was subdivided by isotopic mass balance. The C₄‐derived C in soil microbial biomass was also determined. Additionally, in a root‐exclusion approach, root‐ and SOM‐derived CO₂ were determined by the total CO₂ effluxes from maize (Zea mays L.) and bare‐fallow plots. In both approaches, maize‐derived CO₂ contributed 22% to 35% to the total CO₂ efflux during the growth period, which was comparable to other field studies. In our laboratory study, this CO₂ fraction was tripled due to different climate, soil, and sampling conditions. In the natural‐¹³C‐labeling approach, rhizomicrobial respiration was low compared to other studies, which was related to a low amount of C₄‐derived microbial biomass. At the end of the growth period, however, 64% root respiration and 36% rhizomicrobial respiration in relation to total root‐derived CO₂ were calculated when considering high isotopic fractionations between SOM, microbial biomass, and CO₂. This relationship was closer to the 50% : 50% partitioning described in the literature than without fractionation (23% root respiration, 77% rhizomicrobial respiration). Fractionation processes of ¹³C must be taken into account when calculating CO₂ partitioning in soil. Both methods—natural ¹³C labeling and root exclusion—showed the same partitioning results when ¹³C isotopic fractionation during microbial respiration was considered and may therefore be used to separate plant‐ and SOM‐derived CO₂ sources.     

Identification of carbonate pedofeatures of different ages in modern chernozems

Carbonate pedofeatures of three chernozemic soils developed from loesslike loams in the foreststeppe zone of Lipetsk oblast under fallow plot (Luvic Chernozem (Clayic, Pachic)) and under forest (Calcic Chernozem (Clayic, Pachic)) and in the steppe zone of Dnepropetrovsk oblast (Calcic Chernozem (Episiltic, Endoclayic, Pachic)) were studied in the field and laboratory with the use of a set of methods, including the radiocarbon method, mass spectrometry, and micro- and submicromorphology. The morphological diversity of carbonate pedofeatures in these soils was represented by carbonate veins, coatings, disperse carbonates (carbonate impregnations), soft masses (beloglazka), and concretions. In the forest-steppe soils, disperse carbonates and soft masses were absent. The radiocarbon age of carbonate pedofeatures in the forest-steppe soils varied within a relatively narrow range of 3–4.3 ka cal BP with a tendency for a younger age of carbonate concretions subjected to destruction (geodes). In the steppe chernozem, this range was larger, and the ¹⁴C ages of different forms of carbonate pedofeatures were different. Thus, soft masses (beloglazka) had the age of 5.5–6 ka cal BP; disperse carbonates, 17.5–18.5 ka cal BP; and hard carbonate concretions, 26–27 ka cal BP. Data on δ¹³C demonstrated that the isotopic composition of carbon in virtually all the “nonlabile” carbonate pedofeatures does not correspond to the isotopic composition of carbon of the modern soil organic matter. It was shown that the studied chernozemic soils are polygenetic formations containing carbonate pedofeatures of different ages: (a) recent (currently growing), (b) relict, and (c) inherited pedofeatures. The latter group represents complex pedofeatures that include ancient fragments integrated in younger pedofeatures, e.g., the Holocene soft carbonate nodules with inclusions of fragments of the ancient microcodium.     

Continuous flow isotope ratio mass spectrometry of carbon dioxide trapped as strontium carbonate

Abstract

The isotopic signal provided by differential discrimination against atmospheric carbon dioxide (¹³CO₂) by C₃ and C₄ plant photosynthetic pathways is being widely used to study the processes of carbon (C) fixation, soil organic matter formation, and mineralization in nature. These studies have been facilitated by the availability of automated C and nitrogen (N) combustion analyzers (ANCA) combined with continuous flow isotope ratio mass spectrometers (CFIRMS). Analysis of ¹³CO₂ in these instruments requires consistent sample mass for best precision, a requirement that is easily satisfied for soil and tissue samples by adjusting sample weight. Consistent CO₂ sample size is much more difficult to achieve using gas handling systems for samples of headspace gases when CO₂ concentrations vary widely. Long storage of gaseous samples also is difficult. Extended respiration studies are most easily conducted by trapping CO₂ in alkali and conversion to an insoluble carbonate. Thermal decomposition of the carbonate in an on‐line ANCA allows consistent and optimal CO₂ sample mass to be obtained. The use of precipitated carbonates also facilitates storage of samples and enables full automation of sample analysis using an ANCA interfaced to a CFIRMS. Calcium (Ca), strontium (Sr), and barium (Ba) carbonates were tested. Strontium carbonate (SrCO₃) with the addition of vanadium pentoxide (V₂O₅) as a combustion catalyst was found most suitable.     

Changes in δC composition of soil carbonates driven by organic matter decomposition in a Mediterranean climate: A field incubation experiment

The current view on the relationship between the δ¹³C of pedogenic carbonates and soil organic matter is based on static studies, in which soil profiles are analysed at a given moment of their development. A dynamic approach to this question should also be possible by studying under field conditions how the δ¹³C of carbonates changes as organic matter decomposes. No such study has been undertaken owing to the slowness of the changes in the δ¹³C of carbonates, since it has been calculated that a detectable change will occur only after millenia. Nevertheless, this may not be true where soil CO₂ efflux is intense, as expected in soil zones with high microbial activity. In this paper we test the latter assumption by incubating mixtures of plant material and carbonate-rich red earth in the field at depths of 5, 20 and 40 cm. Four types of plant material were tested: Medicago sativa, Eucalyptus globulus, Quercus ilex and Pinus halepensis. Because the isotopic composition of these plant materials is known, we can determine the isotopic composition of the respired C and study how it relates to the (expected) changes in the δ¹³C. After two years of field incubation, the changes in δ¹³C of carbonates were high enough to be reliably detected and quantified, thus showing that the isotopic composition of soil carbonates can change quite rapidly in biologically active soil horizons. The observed changes are possible only if we assume that the increase in δ¹³C in the overall path respired C → pedogenic carbonate is much higher than the usually applied standard factors (about 15‰). These enrichments can be explained by assuming, as does the currently accepted paradigm, that the precipitation of new carbonates occurs in an open system in which the penetration of free-air CO₂ plays a major role. On the other hand, these enrichments can also be explained by an alternative interpretation, which assumes that the dissolution–precipitation carbonate cycles occur in systems that can be at least temporarily closed. Thus, we suggest that both possibilities (carbonate dissolution and precipitation in either an open or closed system) can coexist in a given soil, even though one or the other will dominate in any given time period.     

The pool of pedogenic carbon in the soils of different types and durations of use as croplands in the forest-steppe of the Central Russian Upland

Based on studying five agrochronoseries, including recent forest (dark) gray soils and soils plowed for 100, 150, and 200–240 and more years in the forest-steppe zone of the Central Russian Upland, the dynamics of the pedogenic carbon pool, including the C_org and C_carb, are considered. In the 2-m-thick layer of the agrogenic soils studied, the pedogenic carbon pool was shown to increase by 15–30% (up to 50%) mainly due to the changes in the C_carb content. The insignificant (by ～10%) growth of the C_org content was found in the soils that were plowed for more than 200–250 years. As the hydrothermal regime changed when passing from the forest to croplands, the C_carb reserves increased due to the ascending of carbonates from the parent rock through the capillary pores, probably, in colloid solution-suspensions. This process proceeded without exchange with the soil CO₂, since the ¹⁴C age and the content of the newly formed carbonates became higher. These carbonates may be called pedogenic-lithogenic agrocarbonates, since they appear in soils as a result of the (agro-) pedogenesis. In this case, their additional source is the lithogenic carbonates, which bring in the “old” carbon. The process of carbonates ascending could be referred to the rapid soil-forming ones with their implementation time being close to ≤50 years.     

Density fractionation of organic matter in dolomite‐derived soils

Dolomite (CaMg(CO₃)₂) constitutes half of the global carbonates. Thus, many calcareous soils have been developing rather from dolomitic rocks than from calcite (CaCO₃)‐dominated limestone. We developed a physical fractionation procedure based on three fractionation steps, using sonication with subsequent density fractionation to separate soil organic matter (SOM) from dolomite‐derived soil constituents. The method avoids acidic pretreatment for destruction of carbonates but aims at separating out carbonate minerals according to density. The fractionation was tested on three soils developed on dolostone parent material (alluvial gravel and solid rock), differing in organic‐C (OC) and inorganic‐C (IC) concentrations and degree of carbonate weathering. Soil samples were suspended and centrifuged in Na‐polytungstate (SPT) solutions of increasing density, resulting in five different fractions: two light fractions < 1.8 g cm^–3 (> 20 μm and < 20 μm), rich in OC and free of carbonate, and two organomineral fractions (1.8–2.4 g cm^–3 and 2.4–2.6 g cm^–3), containing 66–145 mg g^–1 and 16–29 mg g^–1 OC. The organomineral fractions consist of residual clay from carbonate weathering such as clay minerals and iron oxides associated with SOM. The fifth fraction (> 2.6 g cm^–3) was dominated by dolomite (85%–95%). The density separation yielded fractions differing in mineral compositions, as well as in SOM, indicated by soil‐type‐specific OC distributions and decreasing OC : N ratios with increasing density of fractions. The presented method is applicable to a wide range of dolomitic and most likely to all other calcareous soils.     

外加碳酸盐增加石灰性土壤密闭培养过程中CO2的释放量

The closed-jar incubation method is widely used to estimate the mineralization of soil organic C. There are two C pools (i.e., organic and inorganic C) in calcareous soil. To evaluate the effect of additional carbonates on CO2 emission from calcareous soil during closed-jar incubation, three incubation experiments were conducted by adding different types (CaCO3 and MgCO3 ) and amounts of carbonate to the soil. The addition of carbonates significantly increased CO2 emission from the soil; the increase ranged from 12.0% in the CaCO3 amended soil to 460% in the MgCO3 amended soil during a 100-d incubation. Cumulative CO2 production at the end of the incubation was three times greater in the MgCO3 amended soil compared to the CaCO3 amended one. The CO2 emission increased with the amount of CaCO3 added to the soil. In contrast, CO2 emission decreased as the amount of MgCO3 added to the soil increased. Our results confirmed that the closed-jar incubation method could lead to an overestimate of organic C mineralization in calcareous soils. Because of its effect on soil pH and the dissolution of carbonates, HgCl2 should not be used to sterilize calcareous soil if the experiment includes the measurement of soil CO2 production.     

Fertilizer effectiveness of three carbonate apatites on an acid ultisol

Abstract

Two properties that are detrimental to agronomic production with acid tropical soils are elevated aluminum concentrations and low phosphate availability. Direct application of carbonate apatites to acid tropical soils possessing low buffering capacity could possibly resolve this problem. The property that determines the effectiveness of directly‐applied carbonate apatites is the CO₃/PO₄ratio, which indicates the degree of anionic isomorphic substitution occurring within the mineral crystal lattice. Increasing ratios denote greater mineral solubility under acid‐soil conditions. Research was conducted to determine: a) fertilizer efficiency of three carbonate apatites (from North Carolina (NCPR), Central Florida (CFPR), and Kodjari, Upper Volta (KPR)), varying in CO₃/PO₄ratios, to that of triple superphosphate (TSP), and b) liming effects induced by the liberation of carbonates from each source, compared to CaCO₃. Maize (Zea mays L.) was grown in pots containing 3 kg of a Dothan fine sandy loam (fine, loamy siliceous, thermic, Typic Paleudult). Yield was lower from carbonate apatite sources than from TSP during the first cropping period, but was equal to TSP treatments for the second cropping period with rocks possessing a CO₃/PO₄ratio greater than 0.14. The liming effect induced by liberation of carbonates and phosphates from NCPR (400 mg P kg^‐1or 306 mg CO₃kg^‐1) equaled that from CaCO₃(600 mg CO₃kg^‐1) during the first cropping period. Over experimental duration, the soil pH was increased by 0.60, 1.26, and 1.10 pH units with a resulting decrease of 0.13, 0.17, and 0.14 cmol(+) extractable Al kg^‐1by CaCO₃(600 mg CO₃kg^‐1), NCPR (306 mg CO₃kg^‐1), and CFPR (171 mg CO₃kg^‐1), respectively     

Method for 14C‐labeling maize field plots and assessment of label uniformity within plots

Abstract

There is increasing interest in use of isotopic tracers to study nutrient liberation and transformation in plant tissues and soils. We developed a technique for pulse‐labeling plants in the field with ¹⁴C. Spatial distribution of radioactivity was measured in plots of maize (Zea mays L.) plants exposed to ¹⁴CO₂. Two clear polyvinyl chambers measuring 1 m wide × 2 m long × 1 m high were used to ¹⁴C‐ label maize plants in conventional tillage and no‐tillage treatments. A closed loop in‐line with a pump allowed injection of ¹⁴CO₂ and unlabeled CO₂, and subsampling through an infrared gas analyzer. Cooling and mixing of the air within the chambers was achieved through the use of a free‐standing automobile radiator with fan placed in the center of each plot. The specific activities of leaf tips differed by an order of magnitude among maize plants within the plot. Tillage and time after labeling within the first 48 h had no significant effect on specific activity of maize plants. Plant activity significantly differed by row. The row closest to the inlet and along the edge of the chamber was significantly lower in several plots. Despite differences among leaf tip specific activities, total aboveground activity was uniform within the plot. Plant allometry and plant sampling immediately after labeling would help in correcting for within chamber variability in future field labeling studies.     

Short‐term N2O,CO2, NH3 fluxes,and N/C transfers in a Danish grass‐clover pasture after simulated urine deposition in autumn

Urine patches are significant hot‐spots of C and N transformations. To investigate the effects of urine composition on C and N turnover and gaseous emissions from a Danish pasture soil, a field plot study was carried out in September 2001. Cattle urine was amended with two levels of ¹³C‐ and ¹⁵N‐labeled urea, corresponding to 5.58 and 9.54 g urea‐N l^–1, to reflect two levels of protein intake. Urine was then added to a sandy‐loam pasture soil equivalent to a rate of 23.3 or 39.8 g urea‐N m^–2. Pools and isotopic labeling of nitrous oxide (N₂O) and CO₂ emissions, extractable urea, ammonium (NH₄⁺), and nitrate (NO₃^–), and plant uptake were monitored during a 14 d period, while ammonia (NH₃) losses were estimated in separate plots amended with unlabeled urine. Ammonia volatilization was estimated to account for 14% and 12% of the urea‐N applied in the low (UL) and high (UH) urea treatment, respectively. The recovery of urea‐derived N as NH₄⁺ increased during the first several days, but isotopic dilution was significant, possibly as a result of stress‐induced microbial metabolism. After a 2 d lag phase, nitrification proceeded at similar rates in UL and UH despite a significant difference in NH₄⁺ availability. Nitrous oxide fluxes were low, but generally increased during the 14 d period, as did the proportion derived from urea‐N. On day 14, the contribution from urea was 23% (UL) and 13% (UH treatment), respectively. Cumulative total losses of N₂O during the 14 d period corresponded to 0.021% (UL) and 0.015% (UH) of applied urea‐N. Nitrification was probably the source of N₂O. Emission of urea‐derived C as CO₂ was only detectable within the first 24 h. Urea‐derived C and N in above‐ground plant material was only significant at the first sampling, indicating that uptake of urine‐C and N via the leaves was small. Urine composition did not influence the potential for N₂O emissions from urine patches under the experimental conditions, but the importance of site conditions and season should be investigated further.     

Use of C abundance to study short-term pig slurry decomposition in the field

Applying pig slurry (PS) on agricultural soils is a common practice. However, its impact on soil organic C dynamics is not clear. This experiment investigated the use of natural ¹³C abundance to study the short-term C mineralization of anaerobically stored PS under field conditions. Measurements of δ¹³C-CO₂ were made on soil air samples obtained from a bare sandy loam during 22 d following incorporation of either PS alone, PS+barley straw, or barley straw alone; an unamended treatment was used as a control. Slurry C was enriched in ¹³C (−20.0‰) because of the high corn (Zea mays L.) content of the animal diet. This value contrasted with δ¹³C of −28.4‰ for the soil organic matter and of −29.0‰ for the barley straw. A peak of high δ¹³CO₂ values (average of −9.2‰) was observed on the day of PS application and was attributed to the dissociation of PS carbonates when mixed with the relatively acidic soil. After this initial burst, 36% of the evolved CO₂ originated from the decomposing PS. After 22 d of incubation, approx. 20% of the PS-C had been lost as CO₂. This short-term field study did not show any priming effect of PS on the mineralization of straw or native soil C. Due to its heterogeneity, the use of the isotopic composition of the evolved CO₂ for estimating PS decomposition requires precaution either through the use of a specific experimental design involving comparable C3 and C4 treatments, or calculations to account for the presence of ¹³C-enriched inorganic C in the PS.     

Root and rhizomicrobial respiration: A review of approaches to estimate respiration by autotrophic and heterotrophic organisms in soil

Partitioning the root‐derived CO₂ efflux from soil (frequently termed rhizosphere respiration) into actual root respiration (RR, respiration by autotrophs) and rhizomicrobial respiration (RMR, respiration by heterotrophs) is crucial in determining the carbon (C) and energy balance of plants and soils. It is also essential in quantifying C sources for rhizosphere microorganisms and in estimation of the C contributing to turnover of soil organic matter (SOM), as well as in linking net ecosystem production (NEP) and net ecosystem exchange (NEE). Artificial‐environment studies such as hydroponics or sterile soils yield unrealistic C‐partitioning values and are unsuitable for predicting C flows under natural conditions. To date, several methods have been suggested to separate RR and RMR in nonsterile soils: 1) component integration, 2) substrate‐induced respiration, 3) respiration by excised roots, 4) comparison of root‐derived ¹⁴CO₂ with rhizomicrobial ¹⁴CO₂ after continuous labeling, 5) isotope dilution, 6) model‐rhizodeposition technique, 7) modeling of ¹⁴CO₂ efflux dynamics, 8) exudate elution, and 9) δ¹³C of CO₂ and microbial biomass. This review describes the basic principles and assumptions of these methods and compares the results obtained in the original papers and in studies designed to compare the methods. The component‐integration method leads to strong disturbance and non‐proportional increase of CO₂ efflux from different sources. Four of the methods (5 to 8) are based on the pulse labeling of shoots in a ¹⁴CO₂ atmosphere and subsequent monitoring of ¹⁴CO₂ efflux from the soil. The model‐rhizodeposition technique and exudate‐elution procedure strongly overestimate RR and underestimate RMR. Despite alternative assumptions, isotope dilution and modeling of ¹⁴CO₂‐efflux dynamics yield similar results. In crops and grasses (wheat, ryegrass, barley, buckwheat, maize, meadow fescue, prairie grasses), RR amounts on average to 48±5% and RMR to 52±5% of root‐derived CO₂. The method based on the ¹³C isotopic signature of CO₂ and microbial biomass is the most promising approach, especially when the plants are continuously labeled in ¹³CO₂ or ¹⁴CO₂ atmosphere. The “difference” methods, i.e., trenching, tree girdling, root‐exclusion techniques, etc., are not suitable for separating the respiration by autotrophic and heterotrophic organisms because the difference methods neglect the importance of microbial respiration of rhizodeposits.     

Effect of K2SO4 concentration on extractability and isotope signature (δ13C and δ15N) of soil C and N fractions

Determination of the labile soil carbon (C) and nitrogen (N) fractions and measurement of their isotopic signatures (δ¹³C and δ¹⁵N) has been used widely for characterizing soil C and N transformations. However, methodological questions and comparison of results of different authors have not been fully solved. We studied concentrations and δ¹³C and δ¹⁵N of salt‐extractable organic carbon (SEOC), inorganic (N–NH₄⁺ and N–NO₃^?) and organic nitrogen (SEON) and salt‐extractable microbial C (SEMC) and N (SEMN) in 0.05 and 0.5 m K₂SO₄ extracts from a range of soils in Russia. Despite differences in acidity, organic matter and N content and C and N availability in the studied soils, we found consistent patterns of effects of K₂SO₄ concentration on C and N extractability. Organic C and N were extracted 1.6–5.5 times more effectively with 0.5 m K₂SO₄ than with 0.05 m K₂SO₄. Extra SEOC extractability with greater K₂SO₄ concentrations did not depend on soil properties within a wide range of pH and organic matter concentrations, but the effect was more pronounced in the most acidic and organic‐rich mountain Umbrisols. Extractable microbial C was not affected by K₂SO₄ concentrations, while SEMN was greater when extracted with 0.5 m K₂SO₄. We demonstrate that the δ¹³C and δ¹⁵N values of extractable non‐microbial and microbial C and N are not affected by K₂SO₄ concentrations, but use of a small concentration of extract (0.05 m K₂SO₄) gives more consistent isotopic results than a larger concentration (0.5 m ).