Assessment of a sequential extraction procedure for fractionation of soil arsenic in contaminated soils

A sequential fractionation scheme, based on a soil phosphorous fractionation, was developed to assess the chemical nature, and thus the potential bioavailability and mobility of As, at the sites. Soil As was separated into five fractions with (i) anion exchange resin, (ii) NaHCO₃, (iii) NaOH, (iv) HCl, (v) residual. Most sites contained relatively low concentrations of As in the two most labile fractions. The bulk of the contaminant As at the sites seemed to be associated with soil amorphous Fe and Al minerals and the dominant clay minerals which help in As sorption are montmorillonite and mica. Resin-extractable As in particular might provide a good index of potential As bioavailability and mobility.     

离子交换树脂膜测定肥料养分在土壤中的变化

在25℃恒温培养条件下,采用离子交换树脂膜(IERM)连续提取法研究了不同肥料(尿素、氯化钾、磷酸二氢钙、缓释复合肥)养分(氮、磷、钾)在土壤中的变化。结果表明,几种肥料养分释放速率各异,缓释复合肥氮、磷养分释放在前期(28 d)释放较慢。用该方法提取肥料养分(N、P、K)在土壤中的释放累积量随时间的增加而增大,用Elovich、双常数、一级扩散、抛物线扩散4种动力学方程来描述二者的关系,拟合度都达到了极显著水平(r=0.863^**～0.999^**)。用该法测定肥料在土壤中释放养分的变化特性与用其测定的土壤本身养分的变化特性相似。从而提出了离子交换树脂膜法作为一种评价肥料养分在土壤中的变化特性的较理想方法的可能性。     

离子交换树脂膜吸附土壤养分的动力学研究

采用从英国进口的离子交换树脂膜和室内埋置法研究了取自河北玉田县的 4个土壤吸附土壤磷、钾、钙、镁和锰的动力学。结果表明 ,在 0 .5～ 2 4h的吸附时间内 ,随着提取时间的延长 ,树脂膜吸附的土壤磷、钙量和锰量显著增加 ,而吸附的钾量减少。     

Ligno-aliphatic complexes in soils revealed by an isolation procedure: implication for lignin fate

For the last decades, the fate of lignins in soil was analyzed mainly with cupric oxide (CuO) oxidation, which is traditionally used to quantify soil lignin content and characterize its state of degradation. This method presents limitations due to incomplete depolymerization of the lignin structure. In this study, we used a physicochemical soil lignin isolation procedure, which permits recovery of a milled wall enzymatic lignin (MWEL) fraction. Elemental composition and chemical structure of MWEL isolated from plants and soil were characterized. Its incorporation rate into an agricultural loamy soil was studied using stable isotope analyses of MWEL isolated from soils after 0 to 9 years of maize cultivation after wheat. Comparison of MWEL isolated from maize tissues and soil provided information on evolution of the lignin structure once incorporated into soil. We observed aromatic–aliphatic complex formation, which could lead to its sequestration in soil evidenced by increasing MWEL content after 9 years of maize cultivation. The ¹³C natural abundance of isolated MWEL showed faster incorporation of MWEL (17.4 % of renewed lignins after 9 years) compared to total soil organic matter (9 % of total soil organic carbon (SOC) was renewed). This faster incorporation rate of MWEL compared to bulk soil organic matter is in agreement with lignin turnover observed by CuO oxidation. Radiocarbon dating of MWEL suggested a mean age of around 50 years. We conclude that lignin isolation allows (1) access to a different fraction compared to CuO oxidation and (2) a detailed characterization of lignin transformation in soil. We suggest that interaction with aliphatic compounds could be one possible pathway of lignin preservation in soil.     

Washing procedure for mixed‐bed ion exchange resin decontamination for in situ nutrient adsorption

Abstract

Mixed‐bed cation + anion exchange resin bags are frequently used to assess in situ nutrient availability in forest soils, and have demonstrated their utility for comparing the impacts of different disturbances associated with treatments. They are generally installed in organic or mineral soil horizons for a certain time period, then recovered and extracted, to inform about nutrient availability during that period. For the method to be effective, the ion exchange sites of resins must be clear from any contaminants prior to installation in the soil. A washing procedure to be conducted before in situ burial of mixed‐bed resins was developed and is described. The IONAC NM‐60 H⁺/OH^‐ resins are consecutively washed with 2 N NaCl, deionized water, and 0.1 N NaOH. Finally, resins are rinsed with deionized water and stored moist and cold until bag preparation and burial in the soil.     

应用离子交换树脂膜法评价缓释复合肥料供肥特性的研究

在25℃连续恒温培养条件下,采用离子交换树脂膜(IERM)提取,测定了不同缓释复合肥料(SRCF)在土壤中的氮、磷、钾养分的供肥特性,并与盆栽水稻的养分吸收进行比较。结果表明:56.d内2种SRCF在土壤中NO3--N和NH4+-N养分的日均供应量占普通复合肥(NCF)的3.3%～58.1%,并以NH4+-NNO3--N;2种SRCF的H2PO4-和K+的日均供应量占磷、钾施用量分别为NCF的14.9%、23.2%和92.7%、64.5%。与NCF相比,SRCF氮素和磷素养分在土壤中释放具有明显的缓释作用。Elovich和抛物线扩散方程的b值可分别用来表征SRCF的NO3--N、H2PO4-和NH4+-N、K+养分在土壤中释放后被吸收的日均供肥量。用离子交换树脂膜法提取测定的SRCF养分在土壤中的供肥特性与该法测定的土壤本身养分的供肥特性相似。SRCF氮、磷、钾养分累积释放量与盆栽水稻氮、磷、钾养分吸收量呈显著或极显著的正相关(r=0.869～*0.994**)。用离子交换树脂膜提取测定和评价缓释复合肥料在土壤中养分的供肥特性是一种比较理想的方法。     

Speciation of phosphorus in temperate zone forest soils as assessed by combined wet‐chemical fractionation and XANES spectroscopy

Phosphorus availability in terrestrial ecosystems is strongly dependent on soil P speciation. Here we present information on the P speciation of 10 forest soils in Germany developed from different parent materials as assessed by combined wet‐chemical P fractionation and synchrotron‐based X‐ray absorption near‐edge structure (XANES) spectroscopy. Soil P speciation showed clear differences among different parent materials and changed systematically with soil depth. In soils formed from silicate bedrock or loess, Fe‐bound P species (FePO₄, organic and inorganic phosphate adsorbed to Fe oxyhydroxides) and Al‐bound P species (AlPO₄, organic and inorganic phosphate adsorbed to Al oxyhydroxides, Al‐saturated clay minerals and Al‐saturated soil organic matter) were most dominant. In contrast, the P speciation of soils formed from calcareous bedrock was dominated (40–70% of total P) by Ca‐bound organic P, which most likely primarily is inositol hexakisphosphate (IHP) precipitated as Ca₃‐IHP. The second largest portion of total P in all calcareous soils was organic P not bound to Ca, Al, or Fe. The relevance of this P form decreased with soil depth. Additionally, apatite (relevance increasing with depth) and Al‐bound P were present. The most relevant soil properties governing the P speciation of the investigated soils were soil stocks of Fe oxyhydroxides, organic matter, and carbonate. Different types of P speciation in soils on silicate and calcareous parent material suggest different ecosystem P nutrition strategies and biogeochemical P cycling patterns in the respective ecosystems. Our study demonstrates that combined wet‐chemical soil P fractionation and synchrotron‐based XANES spectroscopy provides substantial novel information on the P speciation of forest soils.     

Speciation of 90Sr and other metal cations in artificially contaminated soils: the influence of bone sorbent addition

Purpose

The influence of bone sorbent addition onto distribution of ⁹⁰Sr in artificially contaminated soil was preliminary studied to assess the possibility of biogenic apatite utilization for reduction of ⁹⁰Sr mobility and availability. Simultaneously, the disruption of soil micro- (Cd, Zn, Co, Cu, Cr, and Ni,) and macroelements (Al, Fe, Mn, K, Mg, and Ca) upon Sr contamination and sorbent addition was monitored.

Materials and methods

The model soil was contaminated by inactive Sr, in the form of Sr(NO₃)₂ solution. As a soil additive, sorbent obtained by annealing bovine bones at 400 °C (B400) was applied. Both the uncontaminated and Sr-contaminated soils were mixed with 1, 3, 5, and 10 % of sorbent, suspended in distilled water (initial pH?5; solid/solution ratio, 1:2), and equilibrated for 15 days on a rotary shaker. Solid residues were subjected to modified Tessier five-step sequential extraction analysis, and the amounts of chosen metals in each fraction were determined by inductively coupled plasma–optical emission spectroscopy.

Results and discussion

In the original soil, Sr was mainly found in exchangeable (61 %) and carbonate phase (16 %), whereas after contamination, the content of Sr in exchangeable phase raised to 94 %. With the addition of B400, the decrease in Sr amounts in exchangeable fraction was detected, whereas increase occurred mainly in operationally defined carbonate phase and in the residual. High level of Sr contamination caused the increase in Zn, Ni, Co, Cu, Cd, and Mn and decrease in Ca content in exchangeable phase. Sorbent addition resulted in a migration of these cations to less soluble fractions. This effect was observed even for major soil elements such as Fe, Al, and Mn, regardless of the excessive amounts of Sr in the soil.

Conclusions

Mixing the soil with B400 resulted in reduced Sr mobility and bioavailability. B400 acted as a stabilizing agent for heavy metals, as well. Apatite distinguished selectivity towards heavy metals may interfere with the Sr immobilization and disrupt original cation distribution. Further studies should include more realistic (lower) Sr concentrations in the soil, different soil types, pH, and longer incubation times.     

Arsenic and heavy metal accumulation by Athyrium yokoscense from contaminated soils

Abstract

Athyrium yokoscense, a type of fern that grows vigorously in mining areas in Japan, is well known as a Cd hyperaccumulator as well as a Cu, Pb and Zn tolerant plant. However, no information is available on As accumulation of A. yokoscense, although it often grows on soils containing high levels of both heavy metals and As. In this study, young ferns collected from a mine area were grown in media containing As-spiked soils or mine soil in a greenhouse for 21 weeks. Athyrium yokosense was highly tolerant to arsenate and survived in soils containing up to 500 mg As (V) kg^?1. The addition of 100 mg As (V) kg^?1 resulted in the highest fern biomass (1.95 g plant^?1) among As-spiked soils. Although the As concentration of the fern was lower than other As hyperaccumulators, such as Pteris vittata, A. yokoscense could hyperaccumulate As in mature and old fronds. Arsenic was accumulated most efficiently in old fronds (922 mg kg^?1) in the media containing 5 mg As (III) kg^?1. Moreover, higher As accumulation was found in the roots of the ferns, with a range from 506 to 2,192 mg kg^?1. In addition, in the mine soil with elevated concentrations of As and heavy metals, A. yokoscense not only hyperaccumulated As (242 mg As kg^?1 in old fronds), but also accumulated Cd, Pb, Cu and Zn at concentrations much higher than those reported for other terrestrial plants. Athyrium yokoscense accumulated Cd mostly in fronds in high concentrations, up to 1095 mg kg^?1, while it accumulated Cu, Zn and Pb mainly in the roots and the concentrations were 375, 2040 and 1165 mg kg^?1, respectively.     

Speciation of cadmium,copper, lead,and zinc in contaminated soils

Abstract

To investigate the activity of free cadmium (Cd²⁺), copper (Cu²⁺), lead (Pb²⁺), and zinc (Zn²⁺) ions and analyze their dependence on pH and other soil properties, ten contaminated soils were sampled and analyzed for total contents of Cd, Cu, Pb, and Zn (Cd_T, Cu_T, Pb_T, and Zn_T, respectively), 0.43 MHNO₃‐extractable Cd, Cu, Pb, and Zn (Cd_N, Cu_N, Pb_N, and Zn_N, respectively), pH, dissolved organic matter (DOC), cation exchange capacity (CEC), ammonium oxalate extractable aluminum (Al) and iron (Fe), and dissolved calcium [Ca²⁺]. The activity of free Pb²⁺, Cd²⁺, Cu²⁺, and Zn²⁺ ions in soil solutions was determined using Donnan equilibrium/graphite furnace atomic absorption (DE/GFAA). The solubility of Cd in soils varied from 0.16 to 0.94 μg L^‐1, Cu from 3.43 to 7.42 μg L^‐1, Pb from 1.23 to 5.8 μg L^‐1, and Zn from 24.5 to 34.3 μg L^‐. In saturation soil extracts, the activity of free Cd²⁺ ions constituted 42 to 82% of the dissolved fraction, for Cu²⁺the range was 0.1 to 7.8%, for Pb²⁺ 0.1 to 5.1% and for Zn²⁺2 to 72%. The principal species of Cd, Cu, Pb, and Zn in the soil solution is free metal ions and hydrolyzed ions. Soil pH displayed a pronounced effect on the activity of free Cd²⁺, Cu^2t, Pb²⁺, and Zn²⁺ ions.     

Purification of humic acid by the use of ion exchange resin

Abstract

The humic acid fraction, extracted from soil by alkali or neutral salt solution and acid-recipitated, is generally contaminated with a considerable amount of inorganic matter. The presence of the inorganic matter is often undesirable for studies on humic acid. The inorganic matter is generally taken off by ultrafiltration or electrodialysis. But these methods take time and are unsuitable for the bulk preparation of humic acid.     

Evaluation of an anion exchange resin method for plant available molybdenum in New Zealand soils

Abstract

Molybdenum (Mo) extracted from 31 New Zealand soils by an anion exchange resin method (resin Mo) was compared with that extracted by Tamm's oxalate (oxalate Mo). The amounts extracted by the two methods were correlated but, on average, oxalate Mo was 7 times resin Mo. Resin Mo was correlated with relative yield and Mo uptake of lucerne, although correlations were not high. Oxalate Mo was not correlated with plant data. Inclusion of pH in multiple regressions improved correlations with relative yield for both methods but the prediction equations accounted for only 30–35% of the variation. It is concluded that the resin method, although better than the oxalate method, is not sufficiently accurate for diagnosis of Mo deficiency’ in New Zealand pastoral soils.     

Determination of gypsum and cation exchange capacity in arid soils by a resin method

A simple and direct method for the quantitative determination and removal of gypsum in gypsiferous soil samples was developed. This procedure incorporates a combination of Na- and Cl-resins to aid in the dissolution of the gypsum. The primary effect of the exchange resins is to buffer the composition of the solution and thereby keep the rate of gypsum dissolution high. The dissolved calcium and sulfate exchange with the sodium and chloride on the resins, resulting in a solution containing primarily Na and Cl. The electrical conductivity of the supernatant is directly related to the amount of gypsum dissolved. This method was used on samples of artificially prepared mixtures and naturally gypsiferous soils. Compared with results obtained by other methods, the resin method gave identical results, while requiring much less time and fewer calculations. The resin method was also used to remove gypsum from gypsiferous soil samples prior to CEC determinations to see if the presence of gypsum effects the CEC as determined by the Bower method. No significant effect was noted for soil samples containing less than 20% gypsum.     

固相萃取 -火焰原子吸收光谱法分析水溶肥料铬形态

研究了采用阴离子交换柱吸附 Cr 6+,使之与 Cr 3+分离,火焰原子吸收光谱法测定水溶肥料中水溶态 Cr3+及总铬含量,差减法测得 Cr 6+含量。分析了仪器工作条件、试液上柱流速等对实验结果的影响。结果表明,在最优实验条件下,水溶态总铬测定值的相对标准偏差(RSD)为 1.12%～ 3.13%,水溶态 Cr 3+测定值的 RSD为 1.93%～2.93%;Cr 3+的加标回收率为 98.8%～104.0%,Cr 6+吸附率为 97.0%～102.0%,固相萃取 -火焰原子吸收光谱法可用于水溶肥料中铬形态的检测,且具有成本相对较低、操作简便、重现性好等优点。     

离子交换树脂在土壤养分测试中的研究进展

概述了在农业领域中应用离子交换树脂获取土壤养分含量的研究进展,探讨了树脂的预处理方法、使用形式以及提取土壤养分的基本操作和影响因素,同时提出该技术在提取土壤养分中的应用前景及需要解决的问题。     

复合污染土壤上几种叶类蔬菜对Cd和As的富集效应

[目的]不同蔬菜镉、砷富集系数各异,对镉和砷污染土壤的响应也不同。研究复合污染土壤上不同叶类蔬菜对Cd和As的积累效应,为轻度中度Cd和As污染土壤的合理与安全利用提供适宜的蔬菜种类。[方法]采集了西安市12个污染程度不同的菜地耕层土壤,于2015年3月6日5月26日在西北农林科技大学资源环境学院遮雨大棚内进行了盆栽试验。供试7种叶菜,包括菠菜、油菜、生菜、油麦菜、苋菜、空心菜和茼蒿。蔬菜收获后,测量了蔬菜产量、Cd和As含量与吸收累积量,计算了蔬菜对Cd和As的富集系数等,并用线性回归模型研究了不同蔬菜栽培的土壤Cd和As安全临界值。[结果]镉污染土壤(0.6~2.4 mg/kg)对大多数蔬菜生物量有抑制效应,中、低浓度镉砷复合污染(Cd 1.0~2.4 mg/kg,As 24.9~26.8 mg/kg)对供试蔬菜生长没有叠加效应。镉污染土壤上,菠菜、油菜、苋菜叶、生菜可食部Cd含量均超出食品安全限量标准(0.2 mg/kg),其中菠菜和油菜Cd最高超标4倍以上;而茼蒿和空心菜茎秆Cd未超标。虽然供试蔬菜砷含量随着土壤砷含量增加有升高趋势,但叶菜As含量没有超标。7种蔬菜Cd富集系数为0.083~0.491,高低顺序为油菜、菠菜、生菜和苋菜叶>油麦菜、苋菜茎和空心菜叶>空心菜茎和茼蒿。菠菜、油菜、生菜、油麦菜、苋菜、空心菜和茼蒿土壤Cd安全临界值分别为0.33、0.38、0.46、1.15、0.59~1.79、1.49~8.16和8.98~17.11 mg/kg,其中菠菜、油菜和生菜阈值与现行标准(0.3~0.6 mg/kg)相当,而油麦菜、苋菜、空心菜和茼蒿均大于土壤重金属污染限量值。As富集系数为0.002~0.006,空心菜叶和茼蒿叶片As富集系数显著高于其他蔬菜。7种蔬菜的土壤As临界阈值分别为62.31、70.35、70.21、67.41、67.86~90.43、57.21~75.70和72.43~105.06 mg/kg,均高于现行标准(25 mg/kg)。[结论]中等程度的Cd和As复合污染土壤上,Cd对蔬菜的生长有显著的抑制,As与Cd没有叠加作用。不同蔬菜的产量、污染程度和安全阈值等有显著差异,因此选择低富集、抗污染蔬菜品种是利用中低重金属污染土壤的一条可行途径。空心菜和茼蒿对Cd富集系数低,可推荐在中、低污染土壤上种植。     

Analysis of imazethapyr in agricultural soils by ion exchange membranes and a canola bioassay

Abstract

Because imazethapyr residues in soils may cause plant injury to certain rotational crops, sensitive, and reliable methods for imazethapyr monitoring in soils are needed. In this study, imazethapyr analysis was investigated using two newly developed procedures: an anion exchange membrane extraction followed by an HPLC‐UV detection and a canola bioassay. Nine soils in which no previous application of imazethapyr had been made were collected from farm fields in Saskatchewan, Canada. Soils were spiked to yield imazethapyr concentrations in the range of 0–80 μg kg^‐1 dry soil and were subjected to analysis by the above procedures. In the anion exchange membrane extraction, spiked soils were shaken with the membrane strips; imazethapyr was then eluted from the membranes with a potassium chloride (KC1) solution, partitioned into dichloromethane and injected into the HPLC. This method allowed for the extraction of the ionized portion of imazethapyr from soils. In a laboratory bioassay, pre‐germinated canola seeds were planted in spiked soils and after five days of growth root and shoot growth inhibition was determined. The results of both methods were dependent on soil type. Generally, soils from depressions in the landscape yielded low imazethapyr recovery by anion exchange membrane extraction; these soils also showed low degree of imazethapyr phytotoxicity to canola growth. After imazethapyr field spraying, soils were sampled from the field at different time intervals for up to one year and analyzed in the laboratory by the above methods; also, after one year, a field bioassay was performed. Using the membrane extraction method, imazethapyr was detected only in field samples collected one week after spraying. The membrane extraction method, although very simple and cost‐efficient lacks sensitivity needed for the imazethapyr monitoring at low concentrations in agricultural soils. The 5‐day canola bioassay (root growth inhibition method) was more sensitive than the membrane extraction and showed imazethapyr presence in all field samples. However, because crop growth inhibition was more severe in the field than in the laboratory, a field bioassay may be the most reliable means to assess injury potential for certain sensitive rotational crops under field conditions.     

A survey of symbiotic nitrogen fixation by white clover grown on metal contaminated soils

There is conflicting evidence about toxic effects of heavy metals in soil on symbiotic nitrogen fixation. This study was set-up to assess the general occurrence of such effects. Soils with metal concentration gradients were sampled from six established field trials, where sewage sludge or metal salts have been applied, or from a transect in a sludge treated soil. Additional contaminated soils were sampled near metal smelters, in floodplains, in sludge amended arable land and in a metalliferous area. Symbiotic nitrogen fixation was measured with ¹⁵N isotope dilution in white clover (Trifolium repens L.) grown in potted soil that was not re-inoculated, and using ryegrass (Lolium perenne L.) as reference crop. The fraction nitrogen in clover derived from fixation (N_dff) varied from 0 to 88% depending on soil. Pronounced metal toxicity on N_dff was only confirmed in a sludge treated soil where nitrogen fixation was halved from the control value at soil total metal concentration of 737 mg Zn kg⁻¹, 428 mg Cu kg⁻¹ and 10 mg Cd kg⁻¹. The N_dff was significantly reduced by increasing metal concentration in soils from two other sites where N_dff was low throughout and where these effects might be attributed to confounding factors. No significant effects of metals on N_dff were identified in all other gradients even up to elevated total metal concentration (e.g. 55 mg Cd kg⁻¹). The variation of N_dff among all soils (n=48), is mainly explained by the number of rhizobia in the soil (log MPN, log (cells g⁻¹ soil)), whereas correlations with total or soil solution metal concentrations were weak (R²<0.25). The is significantly affected by the presence or absence of the host plant at the sampling site. No effects of metals were identified at even at total Zn concentrations of about 2000 mg Zn kg⁻¹, whereas metal toxicity could be identified at lower most probable number (MPN) values. This survey shows that the metal toxicity on symbiotic nitrogen fixation cannot be generalized and that survival of a healthy population of the microsymbiont is probably the critical factor.