秸秆生物质炭对淹水砖红壤中Cu^(2+)钝化效果的影响

秸秆生物质炭在旱作条件下可通过络合重金属阳离子、提高土壤pH值等途径降低重金属活性和有效性,但是淹水条件下生物质炭对重金属形态的影响研究较少。以30 g·kg^(-1)施用量将不同温度条件下制备的油菜和花生秸秆生物质炭及商品活性炭添加到广东徐闻砖红壤中,并添加5 mmol·kg^(-1)Cu(NO_3)_2和20 g·kg^(-1)葡萄糖,淹水培养49 d,采用连续提取法分级提取不同形态Cu^(2+)并研究其动态变化。结果表明,添加活性炭、400℃条件下制备的油菜秸秆炭和300、400、500℃条件下制备的花生秸秆炭后,淹水培养初期土壤溶液pH值比对照组明显增加,酸溶态Cu^(2+)含量显著降低,还原态和氧化态Cu^(2+)含量有所升高。随淹水时间增加,土壤pH值逐渐降低,导致生物质炭处理土壤中酸溶态Cu^(2+)含量显著升高,生物质炭对Cu^(2+)的钝化效果逐渐减弱并消失,还原态和氧化态Cu^(2+)含量降低。在49 d培养时间内残渣态Cu^(2+)含量变化不大。淹水条件下生物质炭对砖红壤中Cu^(2+)的钝化效果并不持久,甚至由于生物质炭中有机物质分解而产生更多有机酸,导致淹水后期生物质炭处理砖红壤pH值较对照低,反而提高了Cu^(2+)的活性和生物有效性。

Dissolution of Aluminum in Variably Charged Soils as Affected by Low-Molecular-Weight Organic Acids

Low-molecular-weight (LMW) organic acids exist widely in soils and play an important role in soil processes such as mineral weathering, nutrient mobilization and Al detoxification. In this research, a batch experiment was conducted to examine the effects of LMW organic acids on dissolution of aluminum in two variably charged soils, an Ultisol and an Oxisol. The results showed that the LMW organic acids enhanced the dissolution of Al in the two investigated soils in the following order: citric > oxalic > malonic > malic > tartaric > salicylic > lactic > maleic. This was generally in agreement with the magnitude of the stability constants for the Al-organic complexes. The effects of LMW organic acids on Al dissolution were greater in the Ultisol than in the Oxisol as compared to their controls. Also, the accelerating effects of citric and oxalic acids on dissolution of Al increased with an increase in pH, while the effects of lactic and salicylic acids decreased. Additionally, when the organic acid concentration was less than 0.2 mmol L-1, the dissolution of Al changed little with increase in acid concentration. However, when the organic acid concentration was greater than 0.2 mmol L-1, the dissolution of Al increased with increase in acid concentration. In addition to the acid first dissociation constant and stability constant of Al-organic complexes, the promoting effects of LMW organic acids on dissolution of Al were also related to their sorption-desorption equilibrium in the soils.

Understanding the biochar’s role in ameliorating soil acidity

Extensive acidic soils,which suffer from accelerated soil acidification,are found in southern China.Soil acidity,aluminum toxicity,and nutrient deficiencies severely limited crop productivity in acidic soils.It has been widely reported that crop residue biochars can ameliorate acidic soils and increase crop productivity.Here,we summarized the positive effects and mechanisms involved in the correction of soil acidity,the alleviation of aluminum toxicity and the increase of soil pH buffering capacity by crop residue biochars.The carbonate,oxygen-containing functional groups and silicates in biochars are the major components responsible for their efficacy in amending acidic soils and resisting soil re-acidification.We conclude that application of crop residue biochars may be a better option than traditional liming to ameliorate acidic soils.Nonetheless,further researches into soil acidification are still required to address some issues that are controversial and poorly understood.

Effect of Crop-Straw Derived Biochars on Pb(Ⅱ) Adsorption in Two Variable Charge Soils

Two variable charge soils were incubated with biochars derived from straws of peanut, soybean, canola, and rice to investigate the effect of the biochars on their chemical properties and Pb（II） adsorption using batch experiments. The results showed soil cation exchange capacity （CEC） and pH significantly increased after 30 d of incubation with the biochars added. The incorporation of the biochars markedly increased the adsorption of Pb（II）, and both the electrostatic and non-electrostatic adsorption mechanisms contributed to Pb（II） adsorption by the variable charge soils. Adsorption isotherms illustrated legume- straw derived biochars more greatly increased Pb（II） adsorption on soils through the non-electrostatic mechanism via the formation of surface complexes between Pb（II） and acid functional groups of the biochars than did non-legume straw biochars. The adsorption capacity of Pb（II） increased, while the desorption amount slightly decreased with the increasing suspension pH for the studied soils, especially in a high suspension pH, indicating that precipitation also plays an important role in immobilizing Pb（II） to the soils.

Interactions of Heavy Metal Ions with Paddy Soils as Inferred from Wien Effect Measurements in Dilute Suspensions

Interactions of three heavy metal ions, Cu2+, Cd2+, and Pb2+, and, for comparison, Na+ with electrodialytic clay fractions (less than 2μm in diameter) of four paddy soils as well as a yellow-brown soil as a control soil were evaluated based on measurements of the Wien effect in dilute suspensions with a clay concentration of 10 g kg-1 in four nitrate solutions of 2×10-4/z mol L-1, where z is the cation valence, and a nitric acid solution of 3×10-5 mol L-1.Field strengths ranging from 15 to 230 kV cm-1 were applied for measuring the electrical conductivities (ECs) of the suspensions. The mean free binding energies between the various cations and all of the soils determined from exchange equilibrium increased in the order: Na+ < Cd2+ < Cu2+ < Pb2+. In general, the ECs of the suspensions in the sodium nitrate solution were smaller than those of the suspensions in the heavy metal solutions because of the lower electrophoretic mobility of sodium compared to the divalent cations. In terms of relative electrical conductivity-field strength relationships, relative electrical conductivity (REC) of suspensions containing various cations at field strengths larger than about 50 kV cm-1 were in the descending order: Na+ > Cu2+ > Cd2+ > Pb2+ for all tested soils. A characteristic parameter of the REC-field strength curves,△REG200, REG at a field strength of 200 kV cm-1 minus that at the local minimum of the concave segment of the REC-field strength curves, characterized the strength of adsorption of the cations stripped off by the applied strong electrical field, and for all soils the values of△REC200 were generally in the order: Na+ < Cu2+≤Cd2+≤Pb2+.

Binding and Adsorption Energies of Heavy Metal Ions with Hapli-Udic Argosol and Ferri-Udic Argosol Particles

Gibbs free binding energy and adsorption energy between cations and charged soil particles were used to evaluate the interactions between ions and soil particles.The distribution of Gibbs free adsorption energies could not be determined experimentally before the development of Wien effect measurements in dilute soil suspensions.In the current study,energy relationships between heavy metal ions and particles of Hapli-Udic Argosol(Alfisol)and Ferri-Udic Argosol were inferred from Wien effect measurements in dilute suspensions of homoionic soil particles(<2μm)of the two soils,which were saturated with ions of five heavy metals,in deionized water.The mean Gibbs free binding energies of the heavy metal ions with Hapli-Udic Argosol and Ferri-Udic Argosol particles diminished in the order of Pb^(2+)>Cd^(2+)>Cu^(2+)>Zn^(2+)>Cr^(3+),where the range of binding energies for Hapli-Udic Argosol(7.25-9.32 kJ mol^(-1))was similar to that for Ferri-Udic Argosol(7.43-9.35 kJ mol^(-1)).The electrical field-dependent mean Gibbs free adsorption energies of these heavy metal ions for Hapli-Udic Argosol and for Ferri-Udic Argosol descended in the order:Cu^(2+)≥Cd^(2+)≥Pb^(2+)>Zn^(2+)>Cr^(3+), and Cd^(2+)>Cu^(2+)>Pb^(2+)>Zn^(2+)>Cr^(3+),respectively.The mean Gibbs free adsorption energies of Cu^(2+),Zn^(2+),Cd^(2+), Pb^(2+),and Cr^(3+)at a field strength of 200 kV cm^(-1),for example,were in the range of 0.8-3.2 kJ mol^(-1)for the two soils.

Hydrolysis of Aluminum Ions in Kaolinite and Oxisol Suspensions as Influenced by Organic Anions

To evaluate the role of kaolinite and variable charge soils on the hydrolytic reaction of Al, the hydrolysis of Al ions in suspensions of a kaolinite and an Oxisol influenced by organic anions was investigated using changes of pH, Al adsorption, and desorption of pre-adsorbed Al. Kaolinite and the Oxisol promoted the hydrolytic reaction of Al above a certain initial Al concentration (0.1 mmol L-1 for kaolinite and 0.3 mmol L-1 for the Oxisol). The Al hydrolysis accelerated by kaolinite and the Oxisol increased with an increase in initial concentration of Al and was observed in the range of pH from 3.7 to 4.7 for kaolinite and 3.9 to 4.9 for the Oxisol. The acceleration of Al hydrolysis also increased with the increase of solution pH, reached a maximum value at pH 4.5, and then decreased sharply. Al hydrolysis was promoted mainly through selective adsorption for hydroxy-Al. Soil free iron oxides compensated a portion of the soil negative charge or masked some soil surface negative sites leading to a decrease in Al adsorption, which retarded acceleration to some extent. For the Oxisol organic anions increased the proportion of adsorbed Al3+ in total adsorbed Al with the increase in soil negative surface charge and eliminated or reduced the acceleration of Al hydrolysis. Different organic anions inhibited the hydrolysis of Al in the order: citrate > oxalate > acetate (under initial pH of 4.5). The formation of Al-organic complexes in solution also inhibited the hydrolysis of Al.

不同产地油菜秸秆制备的生物质炭对红壤酸度和土壤pH缓冲容量的影响

【目的】明确不同产地油菜秸秆制备的生物质炭对红壤酸度的改良和土壤pH缓冲容量的提升效果。【方法】将不同添加量的油菜秸秆炭分别与两种酸性红壤混合,然后进行室内培养试验,测定培养实验前后土壤pH、pH缓冲容量、土壤交换性盐基离子和土壤交换性酸。【结果】添加油菜秸秆炭显著提高了土壤的pH、pH缓冲容量、交换性盐基离子含量,显著降低了土壤交换性酸含量。说明添加油菜秸秆炭不仅可以改良红壤酸度,还能提高红壤的抗酸化能力,因而可以减缓土壤的复酸化。生长在碱性土壤上的油菜秸秆制备的生物质炭对红壤酸度的改良效果和对土壤pH缓冲容量的提升效果均优于生长在酸性土壤上的油菜秸秆制备的生物质炭,在5%添加水平下,前者使湖南红壤pH相比对照提高37.4%,后者使该土壤的p H提高22.4%;相应地,2种生物质炭分别使该土壤的pH缓冲容量分别提高41.4%和37.3%。2种油菜秸秆炭对红壤pH和pH缓冲容量的提升效果与其碱含量和表面官能团多少相一致。【结论】碱性土壤上生长的油菜秸秆制备的生物质炭对红壤具有更好的改良效果。

Soil Acidification of Alfisols as Influenced by Tea Cultivation in Eastern China

Soil acidification is an important process in land degradation around the world as well as in China.Acidification of Alfisols was investigated in the tea gardens with various years of tea cultivation in the eastern China.Cultivation of tea plants caused soil acidification and soil acidity increased with the increase of tea cultivation period.Soil pH of composite samples from cultivated layers decreased by 1.37,1.62 and 1.85,respectively,after 13,34 and 54 years of tea plantation,as compared to the surface soil obtained from the unused land.Soil acidification rates at early stages of tea cultivation were found to be higher than those at the later stages.The acidification rate for the period of 0-13 years was as high as 4.40 kmol H + ha ?1 year ?1 for the cultivated layer samples.Soil acidification induced the decrease of soil exchangeable base cations and base cation saturation and thus increased the soil exchangeable acidity.Soil acidification also caused the decrease of soil cation exchange capacity,especially for the 54-year-old tea garden.Soil acidification induced by tea plantation also led to the increase of soil exchangeable Al and soluble Al,which was responsible for the Al toxicity to plants.

Amendment of Acid Soils with Crop Residues and Biochars

The liming potential of some crop residues and their biochars on an acid Ultisol was investigated using incubation experiments. Rice hulls showed greater liming potential than rice hull biochar, while soybean and pea straws had less liming potential than their biochars. Due to their higher alkalinity, biochars from legume materials increased soil pH much compared to biochars from non-legume materials. The alkalinity of biochars was a key factor aflecting their liming potential, and the greater alkalinity of biochars led to greater reductions in soil acidity. The incorporation of biochars decreased soil exchangeable acidity and increased soil exchangeable base cations and base saturation, thus improving soil fertility.

Potential of Industrial Byproducts in Ameliorating Acidity and Aluminum Toxicity of Soils Under Tea Plantation

It is imperative to choose some low cost,available and effective ameliorants to correct soil acidity in southern China for sustainable agriculture.The present investigation dealt with the possible role of industrial byproducts,i.e.,coal fly ash(CFA),alkaline slag(AS),red mud(RM) and phosphogypsum(PG) in correcting acidity and aluminum(Al) toxicity of soils under tea plantation using an indoor incubation experiment.Results indicated that CFA,AS and RM increased soil pH,while PG decreased the pHs of an Ultisol and an Alfisol.The increment of soil pH followed the order of RM > AS > CFA.All the industrial byproducts invariably decreased exchangeable Al and hence increased exchangeable Ca,Mg,K and Na and effective cation exchange capacity.RM,AS and lime decreased total soluble Al,exchangeable Al and organically bound Al.Formation and retention of hydroxyl-Al polymers were the principal mechanism through which Al phytotoxicity was alleviated by application of these amendments.In addition,the heavy metal contents in the four industrial byproducts constituted a limited environmental hazard in a short time at the rates normally used in agriculture.Therefore,the short-term use of the byproducts,especially AS and RM,as amendments for soil acidity and Al toxicity in acid soils may be a potential alternative to the traditional use of mined gypsum and lime.

Use of Alkaline Slag and Crop Residue Biochars to Promote Base Saturation and Reduce Acidity of an Acidic Ultisol

This investigation was conducted by using alkaline slag and crop straw biochars to reduce acidity of an acidic Ultisol through incubation and pot experiments with lime as a comparison. The soil was amended with different liming materials: lime(1 g kg-1),alkaline slag(2 and 4 g kg-1), peanut straw biochar(10 and 20 g kg-1), canola straw biochar(10 and 20 g kg-1) and combinations of alkaline slag(2 g kg-1) and biochars(10 g kg-1) in the incubation study. A pot experiment was also conducted to observe the soybean growth responses to the above treatments. The results showed that all the liming materials increased soil p H and decreased soil exchangeable acidity. The higher the rates of alkaline slag, biochars, and alkaline slag combined with biochars, the greater the increase in soil p H and the reduction in soil exchangeable acidity. All the amendments increased the levels of one or more soil exchangeable base cations. The lime treatment increased soil exchangeable Ca2+, the alkaline slag treatment increased exchangeable Ca2+and Mg2+levels, and the biochars and combined applications of alkaline slag with biochars increased soil exchangeable Ca2+, Mg2+and K+and soil available P. The amendments enhanced the uptake of one or more nutrients of N, P, K, Ca and Mg by soybean in the pot experiment. Of the different amendments, the combined application of alkaline slag with crop straw biochars was the best choice for increasing base saturation and reducing soil acidity of the acidic Ultisol. The combined application of alkaline slag with biochars led to the greatest reduction in soil acidity, increased soil Ca, Mg, K and P levels, and enhanced the uptake of Ca, Mg, K and P by soybean plants.

Effect of Fe/Al Hydroxides on Desorption of K^+ and NH_4^+ from Two Soils and Kaolinite

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.