蔬菜根际环境钒的形态变化及植物有效性

通过盆栽试验和Tessier连续提取法,研究了蔬菜根际和非根际土壤中钒的形态分布与植物有效性。结果表明,钒在根际和非根际土壤中主要以残渣态和铁锰氧化物结合态存在,钒的含量随其形态不同而变化：当土壤中钒添加量从25mg·kg^-1增加到200mg·kg^-1时,根际土壤交换态钒的百分率增加了9．89％,碳酸盐结合态钒增加了9．38％,铁锰氧化物结合态钒增加了9．99％,残渣态钒的百分率下降了33．6％。土壤添加的钒量增加时,钒的迁移能力增强,使蔬菜的生物量显著降低,蔬菜对钒的吸收作用增强：钒添加量从0增至200mg·kg^-1时,蔬菜鲜质量降低了41．65％,而蔬菜中85％以上的钒积累在根部。根际土壤中碳酸盐结合态钒含量对植物的根、茎叶中钒含量有显著影响,碳酸盐结合态钒与蔬菜鲜质量呈显著负相关。     

Speciation of copper in soils and relation with its concentration in fruits

Abstract

Different extraction reagents were studied in soils and the results obtained were compared with copper (Cu) contents of seven type fruits grown in these soils. For fruits, wet and dry ashing methods were applied and acceptable results were obtained by using dry ashing. The speciation is based on the dissolution of the soil samples in HNO₃/H₂O₂, oxalic acid, acetic acid, EDTA and citric acid as extraction reagents at hot and cold conditions. Mean total Cu concentrations for all fruits studied were (mg kg^‐1) in the range of 3.0–7.0 (dried weight basis). Significant positive correlations have been found between Cu contents of various fruits and different extractants studied. Flame atomic absorption spectrometry was used for determination of Cu in digestions. Probable chemical forms of Cu in soils were evaluated.     

Evaluation of Decomposition Procedure to Determine Ba,Co, Cr,Cu, Ni,Mn, V,and Zn Total Content in Soil Samples

Different procedures have been proposed to decompose soil samples. Most of them regard determination with fertility aims. In this case, the contents available to the plants are considered. On the other hand, there are procedures to determine total content. The objective of this work was to propose a new decomposition procedure to determine barium (Ba), cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), nickel (Ni), vanadium (V), and zinc (Zn) total content in tropical soils with high content of oxides and silicate. According to the results, the digestion procedure proposed in this study provided satisfactory results for the contents recovery for the elements Ba, Co, Cr, Cu, Mn, Ni, V, and Zn, above 90%, and the use of inverted aqua regia, hydrogen peroxide (H₂O₂), hydrofluoric acid (HF), pre-digestions and agitation was shown as a new alternative for the high silicate content soil sample total digestion, such as the oxisols.     

Sample oxidation procedures for the determination of chromium and nickel in biological material

Abstract

Sample preparation methods for atomic absorption spectrophotometric analysis of chromium and nickel in biological materials were examined. Radiotracer recovery, precision of analysis and analysis of NBS reference samples were the criteria used. Chromium and nickel in biological materials can be successfully prepared for atomic absorption spectrophotometry by dry ashing with nitric acid treatment of the partially oxidized sample. It was necessary to use at least 5% nitric acid to extract the chromium and nickel from the ash. Vet digestion with nitric acid alone was satisfactory for nickel but not for chromium. Wet digestion gave greater variance and required considerably more time. We found no evidence of loss of chromium by either volatilization or insolubility. Since this method is satisfactory for nickel determination it may be implied that it is also satisfactory for other nonvolatile first transition series elements.     

Comparison of Analytical Methods for Quantifying the Levels of Lead,Cadmium, Chromium,and Nickel in Mineral Fertilizers and Industrial By-products

The control of contaminants in fertilizers and industrial by-products is fundamental to safe food production, and it requires low-cost, reliable test methods. The aim of this study was to evaluate the performance of the USEPA 3051a and alternative analytical methods [concentrated hydrochloric acid (HCl), 10 percent HCl, 10 percent sulfuric acid (H₂SO₄), and 50 mmol L^?1 diethylenetriaminepentaacetic acid (DTPA)] for quantifying the levels of lead, cadmium, chromium, and nickel in zinc and/or copper sources. The sample digestions with concentrated HCl, H₂SO₄, and nitric acid (HNO₃) (USEPA 3051a) were heated. Extraction without heating and stirring was employed in 10 percent HCl and 50 mmol L^?1 DTPA methods. The Graybill’s modified F-test, t-test for mean error, and the linear correlation coefficient analysis were used to compare test method performance. Equivalent results to USEPA 3051a were found with the following methods: DTPA for the extraction of lead in zinc sources and concentrated HCl and H₂SO₄ for the extraction of cadmium and chromium in copper sources. However, the absolute values of cadmium, chromium, and nickel recovered by the use of H₂SO₄ were greater regardless of the source. The greater extraction of contaminants in the evaluated methods suggests that there is need to review the official method if the aim is to quantify the total levels of these elements in raw materials and mineral fertilizers.     

Speciation and Transport of Phosphorus in Source Area Rainfall–Runoff

Phosphorus (P) delivered by urban rainfall–runoff partitions and speciates during the transport process. This study examines transport and speciation of P in rainfall and runoff across 15 wet weather events from a paved source area dominated by biogenic loads and to a lesser degree, anthropogenic loads. The mean and median event-based source area total phosphorus is 3.6 and 3.5 mg/l, respectively. The mean and median event-based source area dissolved fraction (f _d) are 0.31 and 0.32 illustrating that P is predominately bound to particulate matter fractions. The majority of events across the monitoring campaign produce a weak mass-limited transport of dissolved phosphorus (DP). With respect to the DP fraction in runoff (pH range of 6.4 to 8.6), the dominant species are orthophosphates (HPO₄ ^?2 and H₂PO₄ ^?) which account for more than 90% of DP mass. The order of species predominance is consistently HPO₄ ^?2?≈?H₂PO₄ ^??>>?CaHPO₄?>?MgHPO₄. With rainfall pH ranging from 4.2 to 4.9 and a f _d?≈?1.0, H₂PO₄ ^? accounts for 95% to 99% of DP in rainfall. Despite the inherent variability of a large dataset (362 samples across 15 events) the speciation of DP is influenced primarily by pH, with a range from 4.2 (rainfall) up to 8.6 (runoff) that results in an order of magnitude change in P species concentration and determines the order between the dominant orthophosphate species. For this source area, the role of alkalinity, dissolved organic carbon and partitioning on DP speciation are minor compared to the influence of pH.     

Phosphorus Speciation and Nutrient Stoichiometry in the Soil-Plant System During Primary Ecological Restoration of Copper Mine Tailings

The effects of plant vegetation on phosphorus(P) speciation, pH, total carbon concentration, total nitrogen concentration, and alkaline phosphatase activities were investigated to explore the P uptake strategy of plants in low-P soil and to determine the nutrient stoichiometric ratio changes in the rhizosphere of plants(Imperata cylindrica, Miscanthus floridulus, Zoysia sinica, Artemisia lavandulaefolia, Indigofera pseudotinctoria, and Conyza canadensis) which had grown for approximately 15 years in copper mine tailings, East China. The results showed that the average pH values in the rhizosphere decreased by 0.06–1.37 compared with those in the non-rhizosphere. The alkaline phosphatase activities of the rhizosphere were significantly higher than those in the non-rhizosphere.The mean concentrations of aluminum(Al)-and iron(Fe)-bound P and Ca_2-P(CaHPO_4) in the rhizosphere of all plants were 5.4% to 87.7%, 49.2% to 214.2%, and 86.6% to 147.6% higher than those in the non-rhizosphere, respectively. Except for Ca_8-P(Ca_8H_2(PO_4)_6)and Ca_(10)-P(Ca_(10)(PO_4)_6(OH)_2) in the rhizosphere, all kinds of inorganic P forms were negatively correlated with pH. Significant correlation was also observed among the concentrations of dominant forms of inorganic P, C, and N and alkaline phosphatase activities in the rhizosphere. Among the studied species, I. pseudotinctoria showed the most significant effect on enhancing soil available P concentration. The stoichiometric ratios of C:P and N:P were apparently higher in the rhizosphere than the non-rhizosphere, whereas these ratios were far below the ratios commonly observed in Chinese soils. These results indicated that the plant growth effectively affected P fractions possibly by changing pH, C and N concentrations, and alkaline phosphatase activity, in the rhizosphere in copper mine tailings.     

Human health risk assessment associated with Co,Cr, Mn,Ni and V contents in agricultural soils from a Mediterranean site

Potentially toxic element contents in agricultural soils were assessed by comparison with levels recorded in the literature and evaluated using Index of Geoaccumulation (I_geo). The model recommended by United States Environment Protection Agency is applied for the health risk assessment from different exposure pathways. The median values of cobalt (Co), chromium (Cr) and nickel (Ni) exceeds about 2, 3 and 14 times, respectively, the corresponding values given by the Geochemical Atlas of Europe project, however, they present low potential ecological risk. The median values of manganese (Mn) and vanadium (V) are slightly lower than the corresponding values given by the Geochemical Atlas of Europe project. Risk assessment results present negligible health risk to children and adults due to manganese (Mn), nickel (Ni) and vanadium (V) exposure through ingestion of contaminated soil. Only the cobalt (Co) hazard quotient (HQ) and hazard index (HI) for children around two sampling sites exceed the acceptable safe risk level.     

Aluminum speciation in running waters on the Canadian pre-Cambrian Shield: Kinetic aspects

To evaluate the extent to which chemical disequilibrium may exist in stream waters following naturally occurring short-term pH changes, surface water samples were collected from two streams in the Lake Laflamme watershed north of Quebec City, placed in large polyethylene containers and stirred continuously at the in situ temperature; changes in Al speciation were followed with time for up to 24 hr. The original samples were collected during the spring snow-melt period and during summer low flows. In this latter case, a pH depression was induced by artificial acidification (H₂SO₄; pH 4) and changes in Al speciation with time were followed in both the acidified and the unacidified samples. Aluminum speciation as operationally defined did respond to artificial acidification (pH lowered; non-exchangeable and non-extractable Al decreased), and these pH-induced changes occurred rapidly (< 4 hr). During storage of natural water samples at in situ T for up to 24 hr, little change in Al speciation was noted, even in the case of samples collected during spring snow-melt; no clear cases of chemical disequilibrium existed among the studied samples. The distribution of Al among its various physico-chemical forms thus appears to be established within the stream itself; at a given stream sampling point the speciation of A1 will not necessarily reflect its geochemical origins, but rather the prevailing in situ conditions (e.g. pH, ligand concentrations).     

Monitoring Metal Speciation in The rivers Meuse and Rhine Using DGT

Although a number of metal speciation methods are nowadays available, most water quality regulations are based on total metal concentrations. One of the main reasons for the ignorance of speciation is the lack of methods with potentiality for monitoring. Conditions that have to be met by such speciation methods are: simple performance, robust and sufficiently accurate. In this study the potential for monitoring purposes of Diffusive Gradients in Thin films (DGT) is investigated as part of a European project for sensor development for routine prediction of metal biouptake in natural waters. Performance characteristics of DGT have been assessed in experiments under controlled laboratory conditions and during in situ application over 4–9 months under different hydrological conditions in the rivers Meuse and Rhine. Results have been worked out for Cu, Ni and Pb. The study shows that DGT has sufficient potential as a robust tool in routine monitoring to observe trends in water quality. However, it appears that during in situ application of DGT the measurement uncertainty of the results is much larger than under laboratory conditions. The increase in measurement uncertainties will partially be due to uncertainties in some as constant considered factors in the calculation of the DGT concentration. For Cu and Ni, the average values for the reproducibility in the rivers Meuse and Rhine appeared to be 28% and 17%, respectively, whereas under laboratory conditions the reproducibilities for both metals were better than 10%. In the speciation of Cu, Ni and Pb in the rivers Meuse and Rhine, the labile fraction, determined using DGT, decreased in the series Ni, Cu, Pb. The ratio of the non-labile and labile fractions of the metals appeared to decrease with increasing content of Dissolved Organic Carbon (DOC).     

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.     

吉林西部土壤砷的形态分布及其与土壤性质的关系研究

按照生态地球化学土壤样品元素形态分析方法,将土壤无机砷分成水溶态、离子交换态、碳酸盐态、腐植酸结合态、铁锰氧化物结合态、强有机结合态和残渣态。通过对吉林西部36个表层土壤样品的测试,分析了土壤不同形态砷的分布和不同形态砷与土壤性质的关系。研究表明,洮南市不同形态砷的分布为：残渣态（65．30％）〉腐植酸结合态（17．39％）〉铁锰氧化物结合态（10．70％）〉碳酸盐态（2．23％）〉水溶态（2．17％）〉强有机结合态（1．17％）〉离子交换态（1．04％）。通榆县不同形态砷的分布为：残渣态（56．66％）〉腐植酸结合态（23．82％）〉铁锰氧化物结合态（11．08％）〉碳酸盐态（2．81％）〉水溶态（2．18％）〉离子交换态（1．98％）〉强有机结合态（1．46％）。残渣态砷是吉林西部土壤砷的主要形态。土壤水溶态砷和铁锰氧化物结合态砷与土壤pH值皆呈极显著正相关;残渣态砷与土壤有机质皆呈极显著负相关,而与土壤阳离子交换量呈极显著正相关。离子交换态砷、碳酸盐态砷、铁锰氧化物结合态砷和强有机结合态砷与土壤矿质元素的关系不大,而水溶态砷、腐植酸结合态砷和残渣态砷与土壤矿质元素的关系密切。     

Speciation of aluminum in soil environments

Although aluminum (Al) is abundant in soil environments, it is not an essential element and it is toxic to most organisms. Since the toxicity of Al depends on their chemical forms, the importance of Al speciation has been recognized worldwide. Difficulties in Al speciation are caused by the complex coordination chemistry of Al for the hydrolysis and formation of polynuclear species with a variable degree of solubility in aqueous solution. Nondestructive analyses, such as nuclear magnetic resonance (NMR) spectroscopy, could supply primarily im-portant information on the chemical forms of Al and may enable to evaluate the results ob-tained by other methodologies. In the present report, NMR spectral characteristics of environmentally important Al-containing components, such as hydoxyaluminum ions, Alinorganic complexes, Al-organic complexes, and primary and secondary minerals, are summarized for the nuclei of ²⁷Al and ²⁹Si determined by solution NMR and solid-state magic angle spinning (MAS) NMR. Applications of NMR techniques to soil science, including speciation of phytotoxic Al in soil environments and whole soil NMR studies, are described.     

海藻中铬形态和含量的检测分析方法研究

为研究海藻中铬的形态和含量,本试验采用IonPac CG5A(4 mm×50 mm)阳离子色谱柱,考察并优化络合剂的种类和浓度、流动相的种类和浓度、pH值、温度及游离态铬的提取方式等条件对Cr(Ⅲ)和Cr(Ⅵ)分离效果的影响。采用高效液相色谱-电感耦合等离子体质谱(HPLC-ICP-MS)对Cr(Ⅲ)和Cr(Ⅵ)进行分析,并利用电感耦合等离子体质谱(ICP-MS)测定海藻中总铬、结合态铬、游离态铬的含量。结果表明,海藻样品在40℃超声条件下,以5 mmol·L^-1吡啶-2,6-二羧酸(PDCA)的硝酸铵溶液(pH值7.0)为络合剂提取10 min,以50 mmol·L^-1硝酸铵溶液作为流动相,可同时测定海藻中Cr(Ⅲ)和Cr(Ⅵ),该方法操作简单,灵敏度和准确度高。此外,海藻中的铬主要以结合态形式存在,游离态铬的含量较低,且游离态铬以Cr(Ⅲ)形态存在为主。Cr(Ⅵ)形态较少,且含量均低于检出限。本试验通过建立海藻中Cr(Ⅲ)和Cr(Ⅵ)分析方法并对海藻中各种形态铬的含量进行分析检测,为相关标准的制定提供了分析方法和数据支撑。     

Roadside Accumulation of Heavy Metals in Soils in Franklin County,Massachusetts, and Surrounding Towns

Abstract

Metals cycle through the environment, and although many metals are required by biota, several have no known biological function and can be toxic. Metal concentrations [cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), lead (Pb), palladium (Pd), vanadium (V), and zinc (Zn)] are surveyed with an eye toward soil chemistry, environmental and anthropogenic conditions, and potential remediation in 15 locations in and adjacent to Franklin County, MA. Road‐condition information was gathered, soil pH determined, and soils analyzed for soil metal content via a five‐phase sequential extraction and ICP‐AES analyses. Results indicate the majority of similarities are linked to soil pH and soil geochemistry, with only a few metals (Cr, Pb, and Zn) showing clear anthropogenic trends.     

Speciation in metal contaminated soils as revealed by an ion exchange resin membrane fractionation procedure

Abstract

Ion exchangers have proven to be a useful tool in the study of metal speciation in aquatic environments, but have seen little application in the study of metal behavior in soil environments. The labile metal species in polluted soils were evaluated by equilibrating soil suspensions with ion exchange resin membranes of different types at pH values ranging from 3 to 9. The total soluble metal content of cadmium (Cd), chromium (Cr), nickel (Ni), and lead (Pb) contaminated Western Canadian soils was subdivided into (i) low‐pH labile, (ii) weak‐acid labile, (iii) weak‐base labile, (iv) high‐pH labile, and (v) non‐adsorbable forms using cation and anion exchange membranes. Soil suspension is mixed overnight with different types of resin membranes and the cations transferred from the soil are subsequently eluted from the membranes using 1N HCl. The HCl extract is then analyzed for Cd, Cr, Ni, and Pb. The aqueous phase remaining in contact with the soil residue is considered the amount of released non‐labile, non‐adsorbable species. The low‐pH labile fraction constituted the largest proportion of the added metal in poorly buffered (sandy) soils. Weak‐acid and base labile fractions were typically highest in highly buffered soils. Clearly, metal contaminated soils most likely to cause environmental damage are sandy textured soils subject to acidification, although the production of chelating substances by roots and microorganisms may also mobilize considerable quantities of metal in soils of high clay content.     

Chloroform-labile trace elements in soil via fumigation-extraction: Steps towards the soil microbial ionome beyond C:N:P

Secondary and trace elements may be limiting soil microbial functioning, albeit microbial demand and content remain largely unknown and methods for their in situ detection are limited. Thus, the objective of the present study was to take the first step towards the method development for the assessment of the soil microbial ionome, that is, the elemental composition of soil microbial communities. Chloroform (CHCl₃) fumigation extraction was used for the detection of microbial CHCl₃-labile secondary and trace element concentrations in soils. The suitability of two extractants (NH₄NO₃, CaCl₂) for the quantification of CHCl₃-labile concentrations of phosphorus, sulphur, potassium, sodium, and magnesium, as well as selenium, iron, zinc, manganese, copper, cobalt, nickel, molybdenum, vanadium, boron, silicon, barium, arsenic, and cadmium, were tested in six agricultural soils. Additionally, three soil to extractant ratios (1:5, 1:10, and 1:20) and two extraction durations, 1 or 2 h, were tested in a subset of two soils. Out of the two extractants tested, 0.01 M CaCl₂ was found to be the best-suited extractant. For CaCl₂, a soil-to-extractant ratio of 1:20 with an extraction time of 1 h was best for the majority of elements in the two soils tested. In a limited number of agricultural soils, we were able to show that CHCl₃ fumigation extraction can successfully be applied to the elements phosphorus, sulphur, potassium, sodium, magnesium, zinc, manganese, copper, nickel, vanadium, boron, silicon, and barium to yield a CHCl₃-labile element fraction. Conversion values to microbial biomass, accounting for elements contained in the cell envelope components, which are mostly not extractable, and to account for adsorption to soil colloids during extraction are yet to be determined in a larger variety of soils. To overcome some of the limitations of the fumigation extraction approach for secondary and trace elements, a pre-extraction step may provide a suitable solution.     

A simple and inexpensive method for chromium speciation in soil extracts

Abstract

Chromium (Cr) appears in two stable forms in nature as Cr(III) and Cr(VI). Hexavalent chromium (CrO₄ ^2‐; Cr₂O₇ ^2‐) is very toxic and carcinogenic, while inorganic Cr(III), however, is essential for mammals. Only two methods, atomic absorption and inductively coupled plasma atomic emission (ICP) spectrometry, provide information on the total amount of Cr in a test solution. This is the reason that several efforts have been made with regard to Cr speciation. Either an acidic or a basic activated aluminum oxide and a reversed phase C‐18 column or an ion exchanger column are used for the separation of chromium(III) from chromium(VI) in FIA and HPLC analyses. In our experiments, acidic‐activated aluminum oxide was used for separation. This alumina was placed into a silicon tube and connected to an ICP spectrometer between the nebulizer and peristaltic pump. The average grain size of the alumina was large enough that the solution could be pumped through the micro column. Acidic‐activated aluminum oxide in the 2.0 to 8.0 pH range adsorbs the chromate anion but not the Cr(III) cation. During this stage, the Cr(III) content of a sample is measurable. The adsorbed chromate can be eluted with a strong acid. The height or area of the elution peak can be used for the calibration of Cr(VI). Detection limits of 4 μg/kg and 0.5 μg/kg were obtained for Cr(III) and Cr(VI), respectively. The effects of sulphate and phosphate anions on the surface of the alumina on chromate adsorption were also evaluated. This method was used for the measurement of Cr(VI) concentration by 0.01M CaCl₂ extraction of soil.     

上海不同地区土壤中硒的形态分布及其有效性研究

本文研究了上海不同地区土壤中硒的形态分布及其有效性,结果表明,土壤中硒的存在形态与土壤ｐＨ和有机质含量密切相关,土壤中硒主要以有机物－硫化物结合态及元素态存在,占总硒含量在４３～６０％,其次是残渣态,占２３～４３％,而其余三种形态仅占１２～２１％,统计分析表明,可溶态,可交换态及碳酸盐结合态硒对作物最有效,土壤有效硒的ＮａＨＣＯ３和ＫＨ２ＰＯ４浸提法都可以用作判断土壤对作物供硒能力的指标。     

外源砷、铅在三类紫色土中形态分配与其化学、生物有效性研究

对比研究了酸、中、石灰性紫色土添加砷、铅后其形态分配变化及化学、生物有效性特征。试验表明：砷、铅在三种紫色土中形态分配不同，外源砷、铅分配与原始土样本底值有较大差异。从提取能力、生物效应方面比较了几种浸提剂效果，认为：用0.5N NaHCO₃提取As、2.5%HAc提取Pb可以较好地表征3种紫色土砷、铅的有效量。植物吸收砷、铅与土壤有效量有较好的相关性，但吸收形态却因土而异。试验还证明，As的形态分级中H₃BO₃可以很好地掩敝F-对比色的干扰。