超声提取-离子色谱法测定土壤中10种水溶性阴离子

采用超声提取–离子色谱法测定了土壤中F~–、CN~–、BrO_3~–、Cl~–、NO_2~–、Br~–、NO_3~–、PO_4~(3–)、SO_4~(2–)、C_2O_4~(2–)等10种水溶性阴离子含量。样品中阴离子用水浸提,提取条件为:固液比1:10,温度30℃,超声振荡时间30 min。提取完成后离心,取上清液通过0.22μm滤膜过滤后测定。在选定的离子色谱测定条件下,10种被测阴离子的检出限为0.009 7～0.31 mg/kg,不同阴离子的加标回收率为84.0%～112%,相对标准偏差(n=7)为0.09%～4.3%。     

新疆伊犁察南灌区土壤盐分特征

以察南灌区土壤为研究对象,对不同含盐量土壤进行盐化程度分级,并对该地区土壤盐分特征进行相关分析和主成分分析,以及对土壤盐分因子区域影响因素进行探讨。结果表明:察南灌区以碱性土壤为主,HCO_3~–是影响该灌区土壤p H最强的因子;对灌区0~100 cm土体土壤的分析表明,灌区盐化土面积约为总灌溉面积的1/4,盐渍化风险较大;相关性分析显示,HCO–3、Cl~–、SO_4~(2-)、Ca~(2~+)、Mg~(2~+)、Na~+、K~+为盐分主要组成离子,总盐分与各离子之间均呈正相关关系,与总盐分相关性最强的阴离子为SO_4~(2-),相关性最强的阳离子为Mg~(2~+);主成分分析显示,HCO_3~–、Cl~–、K~+为影响该灌区土壤盐分特征的主导因子;通过盐分因子区域影响因素定性分析可知,除HCO_3~–和pH是由河流以及地下水综合作用影响外,其他盐分因子均主要受河流影响。     

基于地理加权回归模型的博斯腾湖湖滨绿洲土壤盐分离子含量高光谱估算

以博斯腾湖湖滨绿洲为研究区,分析HCO_3~–、Cl~–、SO_4~(2–)、Ca~(2+)、Mg~(2+)、Na~++K~+等主要土壤盐分离子含量与土壤高光谱反射率的分数阶微分光谱变换与RSI、DSI、NDSI等二维土壤指数的相关性优选特征波段,构建基于地理加权回归模型的土壤盐分离子含量估算模型。研究结果表明:Na~++K~+的微分变换特征波段集中在468～724 nm与1 182～1 539 nm,二维土壤指数的特征波段集中在1 742～2 395 nm,基于RSI的特征波段优选下地理加权回归模型对Na~++K~+含量的估算效果较好,建模集R~2=0.94,RMSE=0.22,验证集R~2=0.74,RMSE=0.19;SO_4~(2–)含量在1.2阶优选的位于469～636 nm波段估算效果较佳,建模集R~2=0.91,RMSE=0.02,验证集R~2=0.75,RMSE=0.33;Ca~(2+)、Mg~(2+)优选的特征波段主要集中在912～2 340 nm的近红外波段;Cl~–含量在1阶的近红外波段建模效果较好,建模集R~2=0.74,RMSE=0.03,验证集R~2=0.93,RMSE=0.11;含量相对较高的Na~++K~+、SO_4~(2–)、Cl~–的地理加权回归模型精度高于含量较低的Ca~(2+)、Mg~(2+)。     

绿洲盐化潮土有效锌含量与盐分离子的相关性及通径分析

以张掖市甘州区和临泽县绿洲盐化潮土为研究对象,通过采集具有代表性、正常耕作种植、前茬为玉米的典型地块0~20 cm耕层土样分析化验,研究了区域土壤有效锌和盐分离子含量特征,运用通径分析方法研究了它们之间的相关性及不同盐分离子对土壤有效锌含量的影响程度。结果表明,河西绿洲灌区盐化潮土有效锌含量介于0.289~0.736 mg/kg之间,平均为0.473 mg/kg,变异系数为18.68%,超过70%的土壤低于缺锌临界值(0.5 mg/kg),且土壤有效锌含量有随含盐量升高而降低的趋势。土壤有效锌含量与HCO_3~–、Mg~(2+)、Na~+含量之间呈极显著负相关,与Cl~–、Ca~(2+)、K~+含量之间呈显著负相关,与SO_4~(2–)含量之间的相关性不显著。Mg~(2+)对土壤有效锌含量表现出强烈的直接和间接负效应,HCO_3~–表现出很大的直接负效应和强烈的间接正效应,Cl~–、K~+和Na~+均表现出较强的直接和间接负效应,SO_4~(2–)表现出较弱的直接和间接正效应,Ca~(2+)表现出较弱的直接和间接负效应。Mg~(2+)、HCO_3~–和Na~+是影响土壤有效锌含量变化的3个主导因素,对决定系数R~2的贡献超过了68%。     

新疆克里雅绿洲土壤盐分、pH和盐基离子空间异质性分析

以克里雅绿洲盐渍化土壤为研究对象,以野外调查与实地数据为基础,采用空间自相关分析与径向基函数插值法,定量分析了克里雅绿洲土壤的含盐量、pH及盐基离子的空间异质特征。结果表明:绿洲盐渍土表聚性强、呈碱性,土壤含盐量从南至北呈现逐渐增大趋势。土壤含盐量、Na~+、Ca(2+)、K~+、Mg2~+、Cl–、SO_4~(2-)均属于强空间变异,HCO_3~–属于中等强度的空间变异,而pH属极弱变异。土壤盐分含量、pH和盐基离子的Moran’s I指数均通过了显著性检验,研究区土壤含盐量、p H与盐基离子在空间上呈现低聚集性。Pearson相关性分析结果显示,土壤盐分含量与Na~+、K~+、Cl~–和SO_4~(2-)含量具有强正相关性(P0.01),与Ca~(2+)和Mg~(2+)含量中等程度正相关(P0.05);土壤pH与土壤含盐量及盐基离子含量极弱相关。该研究结果可为绿洲水资源合理开发与农业可持续发展提供科学依据,同时可作为盐渍土改良和沙漠化防治等环保工作的决策支撑。     

喀斯特山区不同母质(岩)发育的土壤主要理化性质差异性分析

在贵阳市乌当区采集了白云岩、石灰岩、钙质紫色砂页岩等9种母质(岩)上发育的土壤样品763个,分别进行了土壤主要理化性质的测定和差异性分析。结果表明不同母质(岩)发育的土壤理化性质具有很大的差异:红色粘土、老风化壳和页岩上发育的土壤pH值均为酸性至强酸性,有机质和CEC含量中等,土壤质地较粘重;石灰岩、白云岩和钙质紫色砂页岩上发育的土壤pH值为中性至微碱性,有机质和CEC含量较高,质地较为适中;砂页岩和河流冲积物上发育的土壤pH值为酸性至中性,其余理化性质为中等水平;砂岩发育的土壤pH值为强酸性,其余理化性质均较差。     

熏蒸浸提法测定碱性土微生物生物量碳初探

为探究熏蒸浸提法测定碱性土壤微生物生物量碳(microbial biomass carbon,MBC)的最优熏蒸时间和浸提液浓度,本研究采用9种熏蒸时间、2种K_2SO_4浸提液浓度对不同有机质含量的碱性土壤MBC进行了测定。结果表明:(1)对于碱性土壤,熏蒸时间的选择与土壤有机质含量有关,土壤有机质含量越高,MBC提取值达到稳定的熏蒸时间越长。建议测定高有机质土壤(≥60 g/kg)MBC时熏蒸时间不少于24 h;测定中、低有机质土壤(≤30g/kg)MBC时熏蒸时间不少于18 h。(2)土壤有机质含量影响K2SO4浸提液的提取效率,测定高、中有机质土壤MBC时需要0.5 mol/L K_2SO_4浸提液进行提取;在低有机质土壤MBC测定中,0.25 mol/L K_2SO_4浸提液即可。(3)对于未知有机质含量的碱性土壤建议氯仿熏蒸时间至少为24 h,K_2SO_4浸提液浓度为0.5 mol/L。     

测定土壤硝态氮的紫外分光光度法和镉柱还原法比较

使用改进的紫外分光光度法(校正因素法)和基于镉柱还原的流动注射分析法(镉柱还原法)测定了中国10种不同类型土壤的NO3–-N含量,分析了两种方法的差异性及其适用性。统计分析表明,改进紫外分光光度法与镉柱还原法测定的结果具有极显著的相关性,测定样品的准确度介于89%~104%,具有可比性。在浓度适用上略有差异,对NO3–-N含量极低的土壤样品,采用镉柱还原法可提高精确度;对于NO3–-N含量高的土样选用紫外法可提高测定精确度,测定结果变异性低于镉柱还原法,且紫外法测定值都要高于镉柱还原法。从仪器操作及校准角度来看,紫外法测定操作过程简便,影响因子较少,对NO3–-N批量快速测定更为适用。     

不同年限温室土壤盐分变化及对土壤退化的影响

为明确种植年限与土壤盐分及土壤退化间的关系,选择栽培模式和管理方式相近的温室,研究其土壤盐分、pH和交换性盐基离子随种植年限的变化趋势。结果表明:随种植年限的增加,土壤全盐量增加,第18年达1.833g/kg;土壤K~+和SO_4~(2–)含量升高,Ca~(2+)、Mg~(2+)和HCO_3~–含量降低;土壤中Na~+和Cl~–增量相对较少。土壤盐离子之和占全盐百分比在第6年平均为77.58%,而至第18年时为52.46%,说明随着种植年限延长,土壤盐离子组成已发生较大改变。土壤pH,第18年比第6年平均下降了1.01个单位,土壤交换性盐基下降了20.11%。因而,随温室种植年限延长,土壤盐渍化严重,酸化程度加重,交换能力下降,土壤肥力下降。     

太仓市郊大棚菜地土壤盐分累积与分布特征研究

以太仓市郊大棚菜地土壤为研究对象,研究了太仓市典型大棚菜地土壤盐分累积现状及变化规律。结果表明:太仓市郊大棚菜地土壤全盐含量平均值为3.38 g/kg,已达轻度盐化水平;大棚菜地土壤盐分累积区域分布差异较大,最小值为0.42 g/kg,最大值达12.6 g/kg,变异系数达65.7%;大棚菜地土壤盐分累积量有69.84%超过安全水平,其中51.59%为轻度盐土,10.32%为中度盐土,5.56%为重度盐土;大棚菜地土壤盐分累积分布具有明显的地域性,以浏河镇、沙溪镇和新区发生盐化现象最为严重,盐化土所占比例分别达91.4%、91.0%和83.0%;八大离子组成中,阳离子以Ca~(2+)为主,其次为Na~+和K~+,阴离子以NO_3~–为主,其次为Cl~–和SO_4~(2–);相关性分析表明,影响太仓市郊菜地土壤发生盐化的主要因素是全盐含量、NO_3~–、Cl~–、Ca~(2+)等指标,造成土壤发生次生盐渍化的主要原因是不合理施肥、种植及管理模式等人为外在因素;太仓市郊菜地土壤盐分含量随着大棚种植年限的增加而显著提高,在种植年限为4~5 a时达到峰值,平均值为3.64 g/kg,是种植年限为1 a的大棚土壤含盐量的1.29倍。     

土壤无机阴离子的毛细管电泳分析

采用以铬酸钠为背景电解质、十六烷基三甲基溴化铵为电渗流改性剂的间接紫外检测法电泳系统 ,研究了分离电压、缓冲液的酸碱性等毛细管电泳测定氯离子、硫酸根、硝酸根和磷酸根的基本条件 ,可在 5min内对以上 4个离子实现准确定量。测定了 5个采自全国不同地区的土壤样品水提取液中的无机阴离子。结果显示 ,毛细管电泳可对提取液中的氯离子、硫酸根和硝酸根实现较准确的定量 ,测定结果与离子色谱比较一致 ;对硝态氮的测定结果与KCl提取 流动分析结果相关性达到p <0 10水平 ,表明测定结果可在一定程度上反映土壤氮素养分状况。但土壤用水静止提取 2 4h ,提取液中的磷未达到毛细管电泳和离子色谱法的检测限 ,毛细管电泳的测定精确度不及离子色谱     

某极度酸化的酸性硫酸盐土壤中可溶性和交换性酸的特征

An extremely acidified acid sulfate soil(ASS) was investigated to characterise its soluble and exchangeable acidity,The results showed that soluble acidity of a sample dtermined by titration with a KOH soulution was much significantly greater than that indicated by pH measured using a pH meter,paricularly for the extremely acidic soil samples,This is because the total soluble acidity of the extremely acidic soil samples was mainly composed of various soluble Al and Fe species,possibly in forms of Al sulfate complexes(e.g.,AlSO4^ ) and feerous Fe(Fe^2 )_,It is therefore suggested not to use pH alone as an indicator of soluble acidity in ASS,particularly for extremely acidic ASS,It is also likely that AlSO4^ actively participated in cation exchange reactions.It appears that the possible involvement of this Al sulfate cation in the cation adsorption has significant effect on increasing the amount of acidity being adsorbed by the soils.     

Fractional precipitation of humic acid from colored natural waters

Humic acid (HA) is usually defined in the soil and aquatic sciences as that fraction of base-soluble soil organic matter or dissolved organic matter (DOM) which is insoluble in acid. Stepwise titration of bulk DOM from four samples of bog pore water and stream water were undertaken to study the fractional precipitation of HA. Three independent methods: DOC analysis, absorbance measurements at 330 nm, and densitometry of photographic negatives of filters, were used to quantify the precipitation of HA. Half of the HA which would be precipitable at pH 2.0 can be precipitated at pH values from 3.4 to 4.6. These preliminary results have implications for the stability of DOM in waters that experience pH decreases, and for the capacity of DOM to complex metals.     

Models relating soil pH measurements in water and calcium chloride that incorporate electrolyte concentration

Soil pH is the most routinely measured soil property for assessing plant nutrient availability. Nevertheless, there are various techniques for soil pH measurement, which vary with regard to the solution used and the soil‐to‐solution ratio. Soil pH is commonly measured in water or 0.01 m CaC1₂. Soil pH in CaCl₂ is usually preferred as it is less affected by soil electrolyte concentration and provides a more consistent measurement. Therefore there is a need to convert measurement values between the two methods. Previous models reported linear and curvilinear relationships between the two measurements. However, the pH difference between measurements in water and CaCl₂ is related to the soil solution electrolyte concentration. We observed that the pH difference between the two methods became smaller with increasing soil electrical conductivity (EC). We therefore developed models that relate pH in CaCl₂ and water and incorporate EC values. We calibrated a linear and a non‐linear model (artificial neural networks, ANN) using 9817 soil samples from Queensland, Australia. Soil pH in water and CaCl₂ and EC were measured with a 1:5 soil‐to‐solution ratio. The results show that incorporating EC in the prediction model improves the prediction of pH in CaCl₂ significantly. We validated these models using 4576 independent samples obtained from a diverse range of soils across Australia. Although the linear and ANN models performed similarly, the ANN (which has a curvilinear relationship) provided a better prediction and aligns with the theory that for acid and alkaline pH values, the difference between pH in water and CaCl₂ is less than that for pHs between 4.5 and 7.     

Relationship between chemical and mineralogical properties and the rapid response to acid load of soils in humid Asia: Japan,Thailand and Indonesia

Abstract

It is essential to determine the relationship between soil chemical and mineralogical properties and soil response to acid load to understand the acid-neutralizing capacity and cation behavior of different ecosystems. For 46 soil samples from a subsurface horizon in humid Asia, that is, Japan, Thailand and Indonesia, exchangeable cations, total bases and oxalate-extractable Al (Al_o) were determined, and acid titration was conducted to investigate the rapid soil response to acid load. The acid titration experiment indicated three types of soil response: (1) the release of base cations (particularly Ca and Mg) strongly correlated with exchangeable bases, which dominated the tropical soil samples, (2) the release of Al correlated with Al_o content, which dominated the Japanese soil samples, (3) acid and anion adsorption in soil samples with low acid-neutralizing capacity. To gain further information on the source of soil alkalinity, a column experiment with HCl was conducted using eight selected soil samples in which first-order kinetics were assumed to simulate the time-courses of cation release. In the column experiment, the amounts of Ca and Mg released were close to the exchangeable amounts, and Al_o dissolved more rapidly than Al in crystalline minerals. The rate constants of cation release were large for Ca and Mg, and small for Al, clearly indicating a difference between the exchange and dissolution reactions. Thus, rapid soil response to acid load differed among the soils. A cation exchange reaction was dominant in the tropical soils. In some tropical soils, Ca and Mg were present in exchangeable forms at a higher ratio in the total amounts and they were considered to be easily utilized by plants, but leached out from the soils. In the Japanese soils, including the Andisols, secondary mineral dissolution was conspicuous, resulting in a large acid-neutralizing capacity. In both the tropical and Japanese soils with low acid-neutralizing capacity, anion adsorption mainly contributed to acid neutralization.     

Development of buffer methods and evaluation of pedotransfer functions to estimate pH buffer capacity of highly weathered soils

The pH buffer capacity of a soil (pHBC) determines the amount of lime required to raise the pH of the soil layer from its initial acid condition to an optimal pH for plant growth and the time available under current net acid addition rate (NAAR) until the soil layer acidifies to a critical pH leading to likely production losses. Accurate values of pHBC can also be used to calculate NAAR from observed changes in soil pH. In spite of its importance, there is a critical shortage of pHBC data, likely due to the long period of time needed for its direct measurement. This work aimed to develop quick, simple and reliable methods of pHBC measurement and to test these methods against a slow (7‐day) titration used as benchmark. The method developed here calculates pHBC directly from the pH buffer capacity of the buffer solution and the increase in soil pH and corresponding decrease in pH of the buffer solution following mixing and equilibration. The pHBC values calculated using Adams and Evans or modified Woodruff buffers were in accord with those measured by slow titration. Buffer methods are easily deployed in commercial and research laboratories as well as in the field. The advantage of using buffer solutions to calculate pHBC instead of lime requirement is the broad application of this soil property. The pHBC of a soil is an intrinsic property that would not be expected to need remeasurement over periods of less than decades. Recurring lime requirement can be calculated from the soil's pHBC, initial and target pH values. A large proportion of the variability in pHBC was explained by the soil organic carbon content. This relationship between pHBC and soil organic carbon content allowed us to develop local pedotransfer functions to estimate pHBC for different regions of Australia.     

Isolating the influence of pH on the amounts and forms of soil organic phosphorus

Soil pH influences the chemistry, dynamics and biological availability of phosphorus (P), but few studies have isolated the effect of pH from other soil properties. We studied phosphorus chemistry in soils along the Hoosfield acid strip (Rothamsted, UK), where a pH gradient from 3.7 to 7.8 occurs in a single soil with little variation in total phosphorus (mean ± standard deviation 399 ± 27 mg P kg^?1). Soil organic phosphorus represented a consistent proportion of the total soil phosphorus (36 ± 2%) irrespective of soil pH. However, organic phosphorus concentrations increased by about 20% in the most acidic soils (pH < 4.0), through an accumulation of inositol hexakisphosphate, DNA and phosphonates. The increase in organic phosphorus in the most acidic soils was not related to organic carbon, because organic carbon concentrations declined at pH < 4.0. Thus, the organic carbon to organic phosphorus ratio declined from about 70 in neutral soils to about 50 in strongly acidic soils. In contrast to organic phosphorus, inorganic phosphorus was affected strongly by soil pH, because readily‐exchangeable phosphate extracted with anion‐exchange membranes and a more stable inorganic phosphorus pool extracted in NaOH–EDTA both increased markedly as soil pH declined. Inorganic orthophosphate concentrations were correlated negatively with amorphous manganese and positively with amorphous aluminium oxides, suggesting that soil pH influences orthophosphate stabilization via metal oxides. We conclude that pH has a relatively minor influence on the amount of organic phosphorus in soil, although some forms of organic phosphorus accumulate preferentially under strongly acidic conditions.     

Simultaneous Determination of Low Molecular Weight Organic Acids in Soil Solution by Ion Chromatography

A simple and precise ion chromatographic (IC) method for determination of citric, malonic, succinic, formic, acetic and propionic acids in soil solution was developed. It requires a prior cleanup to the soil solution samples by anion exchange resin (AG1-X8) and determination of organic acids using a Dionex Model 2010i IC. Separation of organic acids by IC permitted their quantitation by conductivity measurements, following suppression of background conductivity by a fiber suppressor. A high degree of precision was achieved in the quantitation of organic acids studied. With the IC method, citric, malonic, succinic, formic, acetic and propionic acids can be determined simultaneously in 16 min. A single operator can analyze about 30 samples in a single working day.     

Some measurements of the pH and chemistry of precipitation at Davis and Lake Tahoe,California

Precipitation samples were collected at Davis and Lake Tahoe, California, in 1972–73 and 1977–78 and analyzed for pH and major cations and anions. Rain and snow in this region of northern California are derived primarily from winter cyclonic storms which move easterly from the Pacific Ocean over Davis and then Lake Tahoe. Precipitation at both sites was found to be more acid than water in equilibrium with atmospheric CO₂. Acidity at Lake Tahoe apparently increased over the 5-yr period of the study. Sulfate was the dominant acid anion in 1972–73 (not measured in 1977–78). A major source of sulfate in precipitation was probably industry in the San Francisco Bay Area, upwind of the study sites. Automobile exhaust emissions throughout the region, which contains three major interstate highways and several large urban centers, contribute both sulfate and nitrate precursors to the atmosphere. As in the Eastern United States, these strong acid anions are influencing precipitation chemistry in northern California, including the Sierra Nevada mountains.     

Temporal changes in chemical properties of air‐dried stored soils and their interpretation for long‐term experiments

The usefulness of stored soils from long‐term experiments is often questioned because of changes that might occur during storage. We examined changes during long‐term storage (8–69 years) in the chemical properties of soils with a range of pH values (3.4–8.1 in water) from woodland and grassland experiments at Rothamsted Experimental Station in the UK. No significant changes during storage were measured for total C and N. Large but erratic changes in exchangeable Na⁺ content between 1959 and 1991 were probably caused by contamination of the 1959 samples by perspiration and from sodium‐based glassware. Exchangeable K⁺ increased during storage but only by a small amount. Small changes in exchangeable Ca²⁺ and Mg²⁺ were measured in some samples but not in others. Generally the amount of exchangeable cations increased slightly during storage. This is probably linked to the decreases of 0.4 units in the pH of acid soils, which we attribute to the hydrolysis of approximately 0.25% of the exchangeable Al³⁺. A doubling of the amount of exchangeable Mn²⁺ during storage for 32 years was probably caused by re‐equilibration of Mn species. The most practicable way to prepare soil samples for long‐term storage is to dry them in air. However, those who study changes in soil by re‐analysing samples of the soil stored for a long time must (i) use the same methods of analysis, or (ii) demonstrate that different methods lead to the same results, and (iii) know what changes can arise during storage.