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Alfalfa is one of the most important and the most cultivated crop due to its high nutritive quality and yield, but adaptation of alfalfa genotypes differ in terms of mobile aluminium stress in the soil. The aim of this study was to evaluate the tolerance to mobile Al concentrations in the laboratory and in the naturally acidic soil and select the promising genotypes based on agro-biological traits. In 2019, a laboratory experiment was conducted at the Institute of Agriculture of LAMMC. The experiment in the acidic soil with different mobile Al concentrations was conducted at the Vezaiciai Branch of LAMMC. In 2020, the crops of alfalfa genotypes (11 cultivars and 3 populations) were established on Balthygleyic Dystric Retisol. The agro-biological traits were assessed during the 2021-2022 season. The tolerance index of hypocotyls and roots was evaluated using the filter-based screening method at different AlCl3 (0.0-64 mM) concentrations. The study results of the filter-based screening method showed that the genotype Zydrune, Malvina, Jõgeva 118, Skriveru, and 3130 were the most tolerant ones and the hypocotyl tolerance index of these genotypes was higher compared to medium tolerant genotypes Birute, PGR12489, Europe and AJ2024 at 8, 16, 32 and 64 mM AlCl3 concentrations. The hypocotyl and root tolerance index of medium tolerant genotypes was higher compared to a sensitive genotype PGR10249 at 8 and 16 mM AlCl3. The study of cluster analysis with mobile Al 0.0-65.0 mg kg-1 showed that the genotypes Zydrune, Europe, AJ2024 and 3130 were the best in terms of wintering and spring regrowth, the cultivar Malvina had the best value of wintering, height before flowering and stem number, the cultivar Birute had the best value of spring regrowth, height before flowering and seed yield, and the cultivar Skriveru had the best value of spring regrowth, height before flowering, stem number and seed yield.

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This study aimed to establish ecotoxicologically acceptable Cu concentrations for soil-residing species by integrating the biotic ligand model and the species sensitivity distribution. Statistical analyses were performed on 35 soil solution samples collected from four distinct land use sites: residential, agricultural, forested, and industrial regions. The environmental parameters of these samples, including pH, dissolved organic carbon (DOC), Ca2⁺, Mg2⁺, K⁺, and Na⁺ concentrations, exhibited wide variations across the four regions. Specifically, pH and the concentrations of Mg2⁺, K⁺, and Na⁺ showed significant variability. Additionally, a strong correlation was observed between pH and Ca2⁺, as well as between the DOC concentration and Mg2⁺ and Na⁺. Using the biotic ligand model, we derived the half-maximal effective activities of Cu (EC50{Cu2+}) for 10 soil organisms based on the chemical compositions of the soil solution samples. Additionally, a species sensitivity distribution approach was employed to determine the 5% hazardous concentration (HC5) for soil biota, which was closely associated with DOC and Na⁺ concentrations, with Mg2⁺ playing a secondary role. We attributed these relationships to the formation of DOC complexes that mitigate Cu toxicity, along with competitive interactions with cations. Notably, HC5 values did not differ significantly across sampling sites (p = 0.523). Clustering based on environmental factors grouped the samples into four clusters, each containing soils from different land use types. However, the third cluster included an outlier from agricultural soil due to its unusually high pH and DOC levels. These findings suggest that it is crucial to consider site-specific soil characteristics when determining ecotoxicologically acceptable Cu concentrations, and soil solution characteristics do not always align with specific land use patterns.

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Northern temperate and boreal forests are large biomes playing crucial ecological and environmental roles, such as carbon sequestration. Despite being generally remote, these forests were exposed to anthropogenic nitrogen (N) deposition over the last two centuries and may still experience elevated N deposition as human activities expand towards high latitudes. However, the impacts of long-term high N deposition on these N-limited forest ecosystems remain unclear. For 18 years, we simulated N deposition by chronically adding ammonium nitrate at rates of 3 (LN treatment) and 10 (HN treatment) times the ambient N deposition estimated at the beginning of the experiment at a temperate sugar maple and a boreal balsam fir forest site, both located in northeastern America. LN and HN treatments corresponded respectively to addition of 26 kgN·ha-1·yr-1 and 85 kgN·ha-1·yr-1 at the temperate site and 17 kgN·ha-1·yr-1 and 57 kgN·ha-1·yr-1 at the boreal site. Between 2002 and 2018, soil solution was collected weekly during summer and concentrations of NO3-, NH4+, Ca2+ and pH were measured, totalling ~12,700-13,500 observations per variable on the study period. N treatments caused soil solution NO3-, NH4+ and Ca2+ concentrations to increase while reducing its pH. However, ion responses manifested through punctual high concentration events (predominantly on the HN plots) that were very rare and leached N quantity was extremely low at both sites. Therefore, N addition corresponding to 54 years (LN treatment) and 180 years (HN treatment) of accelerated ambient N deposition had overall small impacts on soil solution chemistry. Our results indicate an important N retention of northeastern American forests and an unexpected strong resilience of their soil solution chemistry to long-term simulated N deposition, potentially explained by the widespread N-limitation in high latitude ecosystems. This finding can help predict the future productivity of N-limited forests and improve forest management strategies in northeastern America.

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The speciation, bioaccumulation, and toxicity of the newly deposited atmospheric heavy metals in the soil-earthworm (Eisenia fetida) system were investigated by a fully factorial atmospheric exposure experiment using soils exposed to 0.8-year and 1.8-year atmospheric depositions. The results shown that the newly deposited metals (Cu, Cd, and Pb) primarily accumulated in the topsoil (0-6 cm) and were present as the highly bioavailable speciation. They can migrate further to increase the concentrations of Cu, Cd, and Pb in soil solution of the deeper layer (at 10 cm) by 12 %-436 %. Earthworms tended to preferentially accumulate the newly deposited metals, which contributed 10 %-61 % of Cu, Cd, and Pb in earthworms. Further, for the unpolluted and moderately polluted soils, the newly deposited metals induced the significant oxidative stress in earthworms, resulting in significant increases in antioxidant enzyme activities (SOD, CAT, and GSH-Px). No significant differences were observed in the levels of heavy metals in soil solutions, bioaccumulation, and enzyme activities in earthworms exposed to 0.8-year and 1.8-year depositions, indicating the bioavailability of atmospheric metals deposited into soils was rapidly decreased with time. This study highlights the high bioaccumulation and toxicity of heavy metals to earthworm from the new atmospheric deposition during the earthworm growing period.

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Soil solution pH and dissolved organic carbon (DOC) influence cadmium (Cd) uptake by hyperaccumulators but their tradeoff in calcareous soils is unclear. This study investigated the mechanisms of Solanum nigrum L. and Solanum alatum Moench in calcareous soil using a combination of concentration gradient experiments (0.6-100 mg Cd kg-1) and soil solution composition analysis. The results showed that the soil solution pH of S. nigrum remained stable despite Cd stress. On average, the soil solution pH of S. alatum was 0.23 units higher than that of S. nigrum, although pH decreased significantly under high Cd stress. In addition, the concentrations of potassium (K) and calcium (Ca) in the soil solution of S. nigrum increased and decreased under low and high levels of Cd stress, respectively. In S. alatum, the K and Ca concentrations in the soil solution generally increased with increasing Cd stress levels. Moreover, the level of DOC in the soil solution of both plants was higher under Cd stress compared to the control, and a gradually increasing trend with Cd stress level was observed in S. alatum. Consequently, the bioconcentration factors of the roots (2.62-19.35) and shoots (1.20-9.59) of both plants were >1, while the translocation factors were <1, showing an obstacle of Solanum hyperaccumulators in transferring Cd into their aboveground parts. Redundancy analysis revealed that the Cd concentration in S. nigrum roots was significantly negatively correlated with the soil solutions of K and Ca. In contrast, Cd concentrations in S. alatum roots and shoots were significantly positively correlated with soil solution DOC, K, and Ca but negatively correlated with pH. Our results suggest that calcareous soil neutralizes the acidity of released protons but does not affect cation exchange, inhibiting DOC in assisting the translocation of Cd within plants.

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Atmospheric deposition is an important source of heavy metal in agricultural soils, but there is limited research on the mobility of these metals in soil and their impact on soil amendment. Here, we performed a dust incubation experiment in soils in the laboratory and a factorial transplant experiment at three field sites with a gradient of atmospheric deposition to examine the impacts of atmospherically deposited heavy metals (Cu, Cd, and Pb) on the mobility and bioavailability in soils with and without lime applications. Results showed that the atmospherically deposited heavy metals showed high mobility and were primarily presented in the soluble ionic fractions in the wet part and acid-exchangeable and reducible fractions in the dry part of atmospheric deposition. Atmospheric dust addition caused the 2p3/2 and 2p1/2 electrons of Cu atoms in uncontaminated soils to transition the 3d vacant states, resulting in similar copper absorption peaks as atmospheric particles by the observation of X-ray absorption near-edge spectroscopy (XANES). In the field, atmospheric deposition can only increase the mobile fractions in the surface soils, but not in the deeper layers. However, the deposition can increase the soluble and diffusive gradients in thin films (DGT)-measured bioavailable fractions in profile along with the soil depth. Lime applications cannot significantly reduce the mobile fractions of heavy metals in the surface soils exposed to atmospheric deposition, but significantly reduce the heavy metal concentrations in soil solutions and the DGT-measured bioavailable concentrations, particularly in the deeper layer (6-10 cm). The major implication is that atmospherically deposited heavy metals can significantly increase their bioavailable concentrations in the plough horizon of soil and constrain the effects of soil amendments on heavy metal immobilization, thereby increasing the risks of crop uptake.

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We validated a simulation model (PostPLANT-Soil) for predicting pesticide concentrations in succeeding leafy vegetables reported in our first paper in this series, which includes the pesticide sorption process into plant roots. As a result of the model validation with the measured data from a plant uptake study in a growth chamber, the model successfully simulated the concentration changes of pesticides in a plant shoot. However, the simulated shoot concentrations for several pesticides were overestimated compared to the measured values. The leafy vegetable (Brassica rapa) used in this study probably has a high metabolic ability for the fungicide flutolanil from the result of the uptake study under a hydroponic condition.

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Understanding the mechanisms underlying perfluoroalkyl acids (PFAAs) translocation, distribution, and accumulation in wheat-soil ecosystems is essential for agricultural soil pollution control and crop ecological risk assessment. This study systematically investigated the translocation of 13 PFAAs under different iron and nitrogen fertilization conditions in a wheat-soil ecosystem. Short-chain PFAAs including PFBA, PFPeA, PFHxA, and PFBS mostly accumulated in soil solution (10.43-55.33%) and soluble extracellular polymeric substances (S-EPS) (11.39-14.77%) by the adsorption to amino- (-NH2) and hydroxyl (-OH) groups in dissolved organic matter (DOM). Other PFAAs with longer carbon chain lengths were mostly distributed on the soil particle surface by hydrophobic actions (74.63-94.24%). Iron-nitrogen amendments triggered (p < 0.05) soil iron-nitrogen cycling, rhizospheric reactive oxygen species fluctuations, and the concentration increases of -NH2 and -OH in the DOM structure. Thus, the accumulation capacity of PFAAs in soil solution and root EPS was increased. In sum, PFAAs' translocation from soil particles to wheat root was synergistically reduced by iron and nitrogen fertilization through increased adsorption of soil particles (p < 0.05) and the retention of soil solution and root EPSs. This study highlights the potential of iron-nitrogen amendments in decreasing the crop ecological risks to PFAAs' pollution.

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Understanding the sorption behavior of per- and poly-fluoroalkyl substances (PFAS) in soils are essential for assessing their mobility and risk in the environment. Heavy metals often coexist with PFAS depending on the source and history of contamination. In this study, we investigated the effect of heavy metal co-contaminants (Pb2+, Cu2+ and Zn2+) on the sorption of 13 anionic PFAS with different perfluorocarbon chain length (C3-C9) in two soils with different properties. Results revealed that Pb2+, Cu2+ and Zn2+ had little effect on the sorption of most short-chain compounds, while the presence of these heavy metals enhanced the sorption of long-chain PFAS in two soils. The distribution coefficients (Kd) of several long-chain PFAS linearly increased with increasing concentrations of heavy metal, especially in the presence of Pb2+ (ΔKd/Δ [Pb2+] > 3 for PFOS and PFNA vs <1 for PFPeS and PFHxS). While several mechanisms may have contributed to the enhancement of sorption of PFAS, the heavy metals most likely contributed through enhanced hydrophobic interactions of PFAS by neutralizing the negative charge of adsorption surfaces in soils and thus making it more favorable for their partitioning onto the solid phase. Moreover, the increase in the concentrations of heavy metals led to a decrease in the pH of the system and promoted sorption of long-chain compounds, especially in soil with lower organic carbon content. Overall, this study provides evidence that the presence of co-existing heavy metal cations in soils can significantly enhance the sorption of long-chain PFAS onto soil, thereby potentially limiting their mobility in the environment.

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Plastic waste is increasing and is a serious environmental problem. Among the threats associated with plastics is the release of contaminants into the environment. This study aimed to evaluate the efficiency of metals release from plastics (low-density polyethylene (LDPE), polyethylene terephthalate (PET), and polypropylene (PP)) as affected by different soil solution types, artificial root exudates, and distilled water. The extent of metal release varied depending on the type of solution and plastic used. Metals were leached most effectively from plastics in soil solutions, followed by root exudates, and least effectively by distilled water. LDPE released the highest concentrations of Cu and Na into solution, PP released the greatest amount of Fe, and PET released the most Cr. The efficiencies of Mg and Zn release from the plastics (PP and PET) varied by solution type. Among the plastics studied, LDPE exhibited the strongest ability to adsorb metals, such as Fe, Cr, Mg, and Zn from soil solutions. The amount of metal released from the plastics was also dependent on pH, dissolved organic carbon (DOC) concentrations, and the electrical conductivity (EC) of the solutions. Moreover, plastic extracts were found to have negative effects on germination and growth in Lepidium sativum.

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Tungsten (W)-based shots are considered more environmentally safe than lead (Pb)-based shots, but knowledge about the W-shot fate in the soil environment is still limited, especially in terms of minor constituents such as iron, copper, and nickel (Ni). Contaminant behaviour in soil strongly depends on pH; in turn, the corrosion of metal composites may affect the pH locally. The aim of this study was to compare Pb- and W-shot weathering dynamics in soil (silt loam, pH 6.3) and reveal the interplay of shot weathering-induced pH-changes on the mobility of elements using in situ chemical imaging (Diffusive gradients in thin films for labile elements, planar optodes for soil pH) and batch incubation experiments over time (16 months). Despite our expectation to find acidification due to W oxidation, we observed a pH increase by 0.2 units in extracted soil solutions and by 0.6 units in the soil around W-shots as Ni dissolved from the binder phase of the shot. After 10 weeks, release of labile Ni was 3-times higher compared to W despite the low Ni content in the shot (7 %, m/m). Pb-shot oxidation increased soil solution pH by 0.5 units which likely supported mobility of Pb-shot-derived antimony (Sb). Steep gradients of labile W and Pb and soil solution concentrations <0.8 µmol L-1 indicated that transfer from shot to soil was low. Contrastingly, labile Ni and Sb were found up to ~4 mm from the shot surface and in higher soil solution concentrations as suggested by the shot constitution, indicating higher mobility of minor as compared to major shot constituents. After 16 months, 36 % of total Ni were dissolved in the soil solution highlighting the environmental relevance of minor shot constituents in Pb-shot alternatives after short term weathering in soil.

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In order to study the potential of intercropping Pennisetum purpureum Schum with Melia azedarach L. and Broussonetia papyrifera for phytoremediation of heavy-metal contaminated soil around mining areas, a pot experiment was conducted to investigate the effects of intercropping on plant biomass, heavy metal accumulation, dynamic changes in heavy metal content in soil solution, and response characteristics of the rhizosphere microbial community. The results indicated that the shoot biomass of P. purpureum and M. azedarach from their intercropping system (KX) was increased by 26.5% and 13.2%, respectively, and the shoot biomass of B. papyrifera from the intercropping system of P. purpureum and B. papyrifera (GX) was increased by 13.5% compared with their corresponding monoculture systems. The shoot Cd content of M. azedarach in the KX treatment was significantly increased by 24.9% (P<0.05), and their Cd and Pb accumulation in shoots were also significantly increased. The shoot contents and accumulations of Cd and Pb from P. purpureum in the GX treatment were significantly increased; however, those in B. papyrifera shoots were decreased. The total accumulations of Cd and Pb in each pot from intercropping systems were higher than that from the monoculture treatment, with that from the KX treatment being the highest at 1065 µg·pot-1. During the 150-day cultivation process, the pH value and dissolved organic carbon (DOC) content in the soil solution under the intercropping systems of KX and GX were higher than those of original soil (CK). After 150 d cultivation, the DOC contents of the soil solution under the KX and GX treatments were significantly increased by 40.5% and 33.1% in comparison with that under CK (P<0.05), respectively. Compared with those from CK and P. purpureum and B. papyrifera monoculture treatments, the Cd content in soil solution from the KX treatment was significantly decreased by 56.1%, 35.5%, and 46.5%, and that in the GX treatment was decreased by 54.5%, 33.2%, and 44.6% (P<0.05), respectively. The Shannon and Chao1 indices of rhizosphere microorganisms under the intercropping systems were significantly higher than those under CK. The number of unique OTUs in intercropping systems was significantly higher than that in CK and the M. azedarach and B. papyrifera monocultures. Intercropping improved the abundance of dominant bacteria such as Actinobacteriota and Acidobacteriota, and the abundance of Actinobacteriota increased by 31.6%, 20.9%, and 25.3% in the KX treatment and by 32.3%, 21.5%, and 25.9% in the GX treatment, respectively, in comparison with those in CK and the P. purpureum and M. azedarach monocultures. It was concluded that intercropping P. purpureum with wood plants could increase their shoot biomass and the accumulations of Cd and Pb, as well as soil environmental quality, whereas the availability and migration risk of heavy metals in soil were reduced. Moreover, the intercropping of P. purpureum and M. azedarach was more beneficial to the remediation of polymetallic-contaminated soil around mining areas.

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The release of metal-based nanoparticles (MNPs) and nanoplastic debris (NPDs) has become ubiquitous in the natural ecosystem. Interaction between MNPs and NPDs may alter their fate and transport in the sub-surface environment and have not been addressed so far. Therefore, the present study has explored the role of NPDs on the stability and mobility of extensively used MNPs, i.e., CuO nanoparticles (NPs) under varying soil solutions (SS) chemistry. In the absence of NPDs, a very high aggregation of CuO NPs observed in SS extracted from black, lateritic, and red soils, which can be correlated with ionic strength (IS) and type of ionic species. The sedimentation rate (ksed(1/h)) for CuO NPs was >0.5 h-1 in the case of these SS. Interestingly, the stability and sedimentation behavior of CuO NPs varied significantly in the presence of NPDs. The ksed for CuO NPs decreased to half and found <0.25 h-1 in the presence of NPDs in all SS. C/C0 values in breakthrough curves increased drastically (black < alluvial < laterite < red) in presence of NPDs. Results suggest that the release of NPDs in the terrestrial ecosystem is a potential threat leading to increased mobility of MNPs in the environment.

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BACKGROUND: Aluminum (Al) toxicity caused by soil acidification is the main constraint for crop growth in tropical and subtropical areas of southern China. The critical values of soil solution Al3+ activity and pH for crops in acidic soils can provide a useful reference for soil acidity amelioration. RESULTS: A pot experiment in a greenhouse was conducted to investigate the critical values of soil solution Al3+ activity and pH for canola and maize in an Ultisol and an Alfisol. The critical values of soil solution Al3+ activity in Ultisol and Alfisol for canola were 1.5 and 10.0 µmol L-1 , and 13.9 and 30.4 µmol L-1 for maize, respectively. The Al tolerance varied with soil type for the same variety of crop. There was more biomass of roots and shoots and higher plant height under the same Al3+ activity, and thus greater critical values of soil solution Al3+ activity for both crops in Alfisol than those in Ultisol, owing to higher Ca2+ /Al3+ , Mg2+ /Al3+ and K+ /Al3+ ratios in soil solution caused by higher cation exchange capacity and exchangeable base cations in Alfisol, when compared with those in Ultisol. The critical values of soil solution pH for canola and maize in Ultisol were 5.09 and 4.72, respectively; while those in Alfisol were 4.87 and 4.54, respectively. CONCLUSION: The critical values of Al3+ activity were higher for maize than for canola and the critical values for both crops were higher in Alfisol than in Ultisol. The critical soil pH for both crops showed opposite trends to soil Al3+ activity. © 2022 Society of Chemical Industry.

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Rice can simultaneously absorb Fe2+ via a strategy I-like system and Fe(III)-phytosiderophore via strategy II from soil. Still, it remains unclear which strategy and source of Fe dominate under distinct water conditions. An isotope signature combined with gene expression was employed to evaluate Fe uptake and transport in a soil-rice system under flooded and drained conditions. Rice of flooded treatment revealed a similar δ56Fe value to that of soils (Δ56Ferice-soil = 0.05‰), while that of drained treatment was lighter than that of the soils (Δ56Ferice-soil = -0.41‰). Calculations indicated that 70.4% of Fe in rice was from Fe plaque under flooded conditions, while Fe was predominantly from soil solution under drained conditions. Up-regulated expression of OsNAAT1, OsTOM2, and OsYSL15 was observed in the root of flooded treatment, while higher expression of OsIRT1 was observed in the drained treatment. These isotopic and genetic results suggested that the Fe(III)-DMA uptake from Fe plaque and Fe2+ uptake from soil solution dominated under flooded and drained conditions, respectively.

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Cadmium (Cd) and Arsenic (As) in rice grains are a primary exposure source for human beings. However, the simultaneous stabilization of Cd and As in soil becomes difficult due to the opposite properties of those. In this study, we investigated the simultaneous effects of biochar-supported nanoscale zero-valent iron (nZVI-BC) and water management on the decrease of Cd and As bioaccumulation in rice grain. Compared to the control, 0.25-1.00% nZVI-BC coupled with alternate wetting and drying (AWD) management simultaneously decreased the bioaccumulation of Cd and As in rice grains by 15.85-69.16% and 23.06-59.45%, respectively. The cancer risk associated with rice consumption effectively reduced by 15.60-52.41% after the application of nZVI-BC, and the lowest cancer risk was detected in 1.00% nZVI-BC under AWD management. Furthermore, rice cultivated under AWD management had a lower total cancer risk than that cultivated under continuous flooded (CF) management with the same amendment of type and dose. The reduction of soil Cd and As availability and the formation of iron plaque dominated the decrease of Cd and As uptake by rice grains. The elevated soil pH was responsible for Cd adsorption, and the dominant mechanism for As immobilization was the formation of complexes. The iron plaque was double-edged, promoting and inhibiting Cd uptake by rice, wherein the inhibition was predominant under aerobic conditions. In addition, iron plaque was a barrier to preventing the As accumulation by rice, a larger amount of As was immobilized on the iron plaque with nZVI-BC treatment. This study sheds new insights on the simultaneous remediation of Cd and As co-contaminated paddy fields.

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The short-term impact of biomass combustion fly ashes (BAs) fertilization on the spring rape growth, essential and trace elements accumulation in seeds, and selected soil and soil solution properties were analyzed in a pot experiment study. The pot experiment was carried out in the growing season (April-August) during the year 2018. The effect of BAs on the dry matter content in spring rape plants and the relative content of chlorophyll in leaves (SPAD) was analyzed. In addition, the effect of BAs on the accumulation of essential and trace elements in the seeds of this plant was analyzed. The impact of BAs on the basic physicochemical properties of soils was also assessed. Additionally, the solubility of compounds contained in BAs was monitored on the basis of the analysis of the changes in the physicochemical properties of soil solution during the experiment period. The present study demonstrated a positive effect of BAs fertilization on plant growth and development and improvement of soil physicochemical properties. A change has been achieved in the soil reaction class from a slightly acidic (control, NPK) to neutral (D1-D6), with the highest increase in pH induced by the highest ash dose of 3 mg ha-1 (D6). It was shown that BAs contributed to a significant increase in the content of macroelements than trace elements in the analyzed soil. In turn, the accumulation of these elements in plant seeds exhibited an inverse relationship, which was mainly influenced by the soil pH and the content of N, Ca, Mg, K, and Na in the soil, as indicated by the correlation coefficients. The highest contents of Fe, Mn, Zn, Cu, Cr, and Ni were detected in the seeds of plants fertilized with BAs at a dose of 2.0 Mg ha-1 (D4), and their respective values were 263, 363, 107, 51, 1835, and 137% higher than in the control. The Ca, Mg, S, and Na compounds introduced with BAs exhibited high solubility, as evidenced by the higher concentration of Ca2+, Mg2+, Na+, and SO42- ions in the soil solutions and the dynamic changes in pH and EC observed during the experiment. The lowest solubility after the application of BAs was exhibited by N and P. The conducted PCA analysis to a large extent explained the variability between the applied fertilization and the factors analyzed in the experiment. Despite the positive impact of ashes, attention should be paid to the potential risks associated with their use. The use of higher doses of BAs may result in excessive alkalization and salinity of soils and may enhance the accumulation of trace elements in plants. These aspects should therefore be closely monitored, especially in the case of a long-term application of these wastes, in order to avoid serious environmental problems.

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Hydroxyapatite (HAP) can effectively immobilize soil heavy metals, but excess phosphate would be released to aquatic ecosystem, resulting in eutrophication. This study investigated the effects of ferrihydrite (FH) on the HAP immobilization of copper (Cu) and cadmium (Cd) and their reduction of phosphorus release under flooding-drainage alternation conditions. Results showed that the incorporation of HAP and FH significantly increased soil solution pH and decreased Cu2+ and Cd2+ concentrations. Applications of FH, HAP, and FH-HAP (FH and HAP combination) can all enhance soil pH and reduce CaCl2-extractable and exchangeable Cu and Cd, but HAP addition increased soluble phosphate by 6.60-7.77 times compared to control. However, FH-HAP application can significantly reduce phosphate release by 92.7-99.7% compared to HAP application. FH-HAP was the most effective to reduce exchangeable Cu and Cd by 49.8-93.4% and 50.9-88.8% and decreased labile and moderately labile phosphorus by 34.0-74.4% and 13.5-18.6%, respectively, while increased stable phosphorus by 22-45.1% than single HAP. All FH treatments significantly increased amorphous iron oxides by the factors of 4.66-20.8, but only 3% and 5% of FH applications slightly enhanced crystal iron oxides by the factors of 0.81-1.27. The major implication is that the combination of FH and HAP can not only immobilize of Cu and Cd, but also reduce the risk of phosphate release by HAP addition.

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Amelioration and remediation technology was developed for phosphogypsum utilization in Haplic Chernozem of South-European facies (Rostov Region). The technology comprises phosphogypsum dispersed application into the soil layer of 20-45 cm during intra-soil milling. In the model experiment, the phosphogypsum doses 0 (control), 10, 20, and 40 t ha-1 were studied. The Cd thermodynamic forms in soil solution were calculated via the developed mathematical chemical-thermodynamic model and program ION-3. The form of ion in soil solution (or water extract) was considered accounting the calcium-carbonate equilibrium (CCE) and association of ion pairs CaCO30; CaSO40, MgCO30, MgSO40, CaHCO3+, MgHCO3+, NaCO3-, NaSO4-, CaOH+, MgOH+. For calculation of the equilibrium of microelements concentration in soil solution ion including heavy metals (HMs), the coefficient of microelement association kas was proposed. According to calculations, Cd2+ ion in soil solution was mostly bounded to associates CdOH+, partly to associates CdCO30 and CdHCO3+. The calculated kas of Cd was 1.24 units in the control option of experiment and decreased to 0.95 units at phosphogypsum dose 40 t ha-1. The ratio of "active [Cd2+] to total Cd" reduced from 33.5% in control option to 28.0% in the option of phosphogypsum dose 40 t ha-1. The biogeochemical barrier for penetration of HMs from soil to plant roots was high after application of phosphogypsum. According to calculation by ION-3, the standard soil environmental limitations overestimate the toxicity of Cd in soil solution. New decision for intra-soil milling and simultaneous application of phosphogypsum was developed to provide the environmentally safe waste recycling.

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AIMS: Organic acid exudation by plant roots is thought to promote phosphate (P) solubilisation and bioavailability in soils with poorly available nutrients. Here we describe a new combined experimental (microdialysis) and modelling approach to quantify citrate-enhanced P desorption and its importance for root P uptake. METHODS: To mimic the rhizosphere, microdialysis probes were placed in soil and perfused with citrate solutions (0.1, 1.0 and 10 mM) and the amount of P recovered from soil used to quantify rhizosphere P availability. Parameters in a mathematical model describing probe P uptake, citrate exudation, P movement and citrate-enhanced desorption were fit to the experimental data. These parameters were used in a model of a root which exuded citrate and absorbed P. The importance of soil citrate-P mobilisation for root P uptake was then quantified using this model. RESULTS: A plant needs to exude citrate at a rate of 0.73 µmol cm-1 of root h-1 to see a significant increase in P absorption. Microdialysis probes with citrate in the perfusate were shown to absorb similar quantities of P to an exuding root. CONCLUSION: A single root exuding citrate at a typical rate (4.3 × 10-5 µmol m-1 of root h-1) did not contribute significantly to P uptake. Microdialysis probes show promise for measuring rhizosphere processes when calibration experiments and mathematical modelling are used to decouple microdialysis and rhizosphere mechanisms.