Multi-element analysis of soils and sediments by wavelength-dispersive X-ray fluorescence spectrometry

Soil and sediment reference materials were used to calibrate and evaluate an analytical method for the determination of major (Si, Al, Fe, Mg, Ca, Na, K, Mn, P, Ti) and trace elements (As, Ba, Cd, Co, Cr, Cu, Ga, Mo, Mb, Ni, Pb, Rb, S, Sb, Sn, Sr, Th, U, V, Y, Zn, Zr) by sequential wavelength X-ray fluorescence spectrometry. Samples were prepared as pressed pellets and analysis was done with a total measuring time of thirty minutes per sample. Special attention was given to the selection of the thirty reference materials used for calibration of the spectrometer. Another set of eleven RM (reference materials) was analyzed for the evaluation of accuracy. Detection limits for trace elements (1-2 mg kg^-1) are adequate both for geochemical and environmental purposes, except for Cd and Sb. Accuracy for trace elements falls within the expected interval of certified or recommended values in most cases, but for some major elements, like SiO₂, some results showed discrepancies, evidencing difficulties associated with the determination of light elements in complex matrices. But when quality criteria proposed by mapping programs are applied to the results, their requirements are fulfilled. Both instrumental precision, obtained by twelve sample replicate analyses, and analytical precision, considering also sub-sampling and pellet preparation, lie between the limits of the Horwitz expression, except at concentrations close to the detection limits.     

全自动消解-电感耦合等离子体质谱法测定环境土壤中13种元素

建立了全自动消解-电感耦合等离子质谱法(ICP-MS)测定环境土壤中13种常见元素的新方法。确定的最佳实验条件如下:采用标准模式测定铅、镍;采用碰撞模式,以氦气流速为3.0 mL/min测定铍、锰、钴、铜、锌、钼、镉、钡、铊、铬、锑。通过内标校正土壤基体干扰,编辑干扰元素校正方程校正质谱干扰,各个元素校准曲线的线性相关系数>0.999 9,方法检出限在0.007～0.5μg/g之间,该方法用土壤标准物质GSS-13进行验证,1.05%～4.91%之间,13种元素的加标回收率89%～127%,各元素的测定值与标准值吻合。以吉林市农用地土壤为实际测定对象,加标回收率88%～134%,利用电感耦合等离子体发射光谱法(ICP-AES)进行仪器比对,结果基本一致。     

Oxidation and fate of chromium in soils

Abstract

The ammonia electrode method was used to characterize soil organic nitrogen. Amide-N, α-amino-N and hexosamine-N were estimated by measuring the ammonium-N derived from each organic-N with an ammonia electrode after hydrolysis of standard compounds followed by certain treatments. Each organic-N was recovered quantitatively from each standard compound in the presence and absence of soil. Twenty soil samples were analyzed for the above forms of organic nitrogen by both the distillation and electrode methods. The results obtained by the ammonia electrode method for each form of organic nitrogen agreed closely with those obtained by the distillation method. The electrode method was preferred for subsequent soil studies since it is simple and sensitive.     

Stabilization of chromium(VI) by hydroxysulfate green rust in chromium(VI)-contaminated soils

Chromium (Cr)-contaminated soils pose a great environmental risk, with high solubility and persistent leaching of Cr(VI). In this study, hydroxysulfate green rust (GR_SO4), with the general formula Fe(II)₄Fe(III)₂(OH)₁₂SO₄·8H₂O, was evaluated for its efficiency in Cr(VI) stabilization via Cr(VI) reduction to Cr(III) in four representative Cr(VI)-spiked soils. The initial concentrations of phosphate buffer-extractable Cr(VI) (Cr(VI)_b) in soils 1, 2, 3, and 4 were 382.4, 575.9, 551.3, and 483.7 mg kg^-1, respectively. Reduction of Cr(VI) to Cr(III) by structural Fe(II) (Fe(II)_s) in GR_SO4 in all studied soils was fast, wherein the application of GR_SO4 markedly decreased the amount of Cr(VI)_b at the Cr(VI)_b/Fe(II)_s stoichiometric mole ratio of 0.33. The kinetics of Cr(VI) reduction by GR_SO4 could not be determined as this reaction coincided with the release of Cr(VI) from soil during the experiment. The concentration of Cr(VI)_b decreased, as the Cr(VI)_b/Fe(II)_s ratio decreased from 0.46 to 0.20, generally to below 10 mg kg^-1. Back-transformation of the generated Cr(III) was examined in the presence of manganese oxide birnessite at the birnessite/initial Cr(III) mole ratio of 4.5. The results of batch tests showed that only 5.2% of the initial Cr(III) was converted to Cr(VI) after two months, while under field capacity moisture conditions, less than 0.05% of the initial Cr(III) was oxidized to Cr(VI) after six months. The results illustrated that remediation of Cr(VI)-contaminated soils would be fast, successful, and irreversible with an appropriate quantity of fresh GR_SO4.     

营养型土壤改良剂对酸性土壤中钾的调节及玉米吸钾量的影响

营养型土壤改良剂(以下简称改良剂)施入三种不同肥力水平的土壤进行恒温培养试验和盆栽试验,测定土壤有效钾的含量、盆栽试验玉米的生物量和钾吸收量。结果表明:对于有效钾含量高的土壤,改良剂能促进钾的缓效化,有利于土壤钾的保蓄,防止土壤钾的淋失;对于有效钾含量较低的土壤,改良剂可以活化土壤中的钾,提高土壤钾的有效性;不同肥力水平的土壤,改良剂都能促进玉米对钾的吸收,有利于提高钾肥的吸收利用效率。     

熔融制样—X射线荧光光谱法快速测定复合肥中的磷、钾、钙、镁、锰、铁、铜、钠、锌和铝

为实现复合肥样品中多元素的同时分析,采用熔融片法制样,有效地消除了试样的粒度效应,用X射线荧光光谱法测定复合肥样品中磷、钾、钙、镁、锰、铁、铜、钠、锌和铝10个元素,对仪器工作条件进行了试验并选定最佳条件,使各元素测定所要求的灵敏度和准确度得到满足,以8个合成的样品作为校准样品,采用固定理论α影响系数进行回归及基体效应校正,方法精密度(RSD,n=8)≤1.36%,分析结果与化学法进行对照基本一致。     

Indicative properties of fly‐ash affected forest soils in Northeastern Germany

Many forest ecosystems in Germany are strongly influenced by emissions of pollutants like SO₂ and alkaline dusts. To quantify and evaluate the consequences of long‐term fly ash deposition on forest soils, a study was conducted in pine stands (Pinus sylvestris) in the Dübener Heide in Northeastern Germany. This forest area has been influenced mainly by emissions from coal‐fired power plants and the chemical industry of the industrial region Bitterfeld‐Wolfen‐Zschornewitz since the early 1900. The study sites are located along a fly ash deposition gradient of 8, 16, 14, 18, and 25 km away from the main emission source in Bitterfeld (sites 1, 2, 3, 4, and 5, respectively). Samples of the organic horizons (Oi, Oe, and Oa) and mineral topsoil (0—10 cm) were taken in fall 1998 and analyzed for their ferromagnetic susceptibility and total ash content. Scanning electron microscopy (SEM) and energy dispersive X‐ray microanalysis (EDX) were performed on selected samples to differentiate between the pedogenic and atmospheric origin of the mineral components in the organic horizons. As a result of the long‐term deposition, ferromagnetic fly ash components are mainly accumulated in the Oe and Oa horizons of the forest soils studied. Ferromagnetic susceptibility was significantly higher (p ≤ 0.05) in the Oe horizon of sites 1 and 2 compared to sites 3, 4, and 5. Unusually high total ash contents for organic horizons of > 74 % were determined in the Oa at all sites. SEM revealed 3 distinct features of persistent fly ash deposits from coal‐fired power plants within the organic horizons that can be defined as ”︁stable glasses” with magnetic properties, aluminum‐silicate‐minerals, and slag fragments. SEM and EDX indicated that a great portion of the mineral particles found in the organic horizons of forests soils influenced by fly ash are from atmospheric sources. For detection of atmospheric lignite‐derived deposition into forest soils, the Oe and Oa horizons have to be considered as specific diagnostic horizons because they show indicative properties for such soils.     

Comparison of methods for measuring heavy metals and total phosphorus in soils contaminated by different sources

The relationships between the concentrations of zinc (Zn), lead (Pb), copper (Cu), nickel (Ni) and chromium (Cr) as measured by X-ray fluorescence analysis (XRF), aqua regia, and HNO₃ pressure digestion were studied in soil samples covering a wide range of heavy metal concentrations. The soils were contaminated by sewage sludge, exhaust depositions, river sediments of mining residues, and dump material. The question was addressed whether the source of heavy metals or other soil properties affect the relationship between these three methods. The aqua regia-digestible fraction of the five heavy metals reached on average 64% of the XRF-detectable content. The pressure accelerated HNO₃-digestible fraction of the five heavy metals was on average 71% of the XRF-detectable content; the respective phosphorus (P) fraction reached a median of 75%. This suggests that HNO₃ pressure digestion can also be used for characterizing the total P content of soils. Aqua regia extraction and HNO₃ pressure digestion gave similar values for Zn, Pb, and Cu, which dominate the heavy metal load of most contamination sources. Significantly higher Cr values were obtained by HNO₃ pressure digestion than by aqua regia extraction. Additionally, the Cr contents were affected by the source, e.g. sewage sludge had relatively high contents of aqua regia and HNO₃ pressure extractable contents in comparison to the XRF values. The element-specific relationships between the three methods were all highly significant. However, the respective multiple linear regression models were in most cases affected by soil organic carbon (C), in some cases by clay or soil pH.     

污水处理反硝化除磷-诱导结晶磷回收工艺中除磷微生物特性

为探究反硝化除磷-诱导结晶磷回收工艺中缺氧池污泥释磷、吸磷以及微生物特征,利用荧光原位杂交（fluorescence in situ hybridization,FISH）技术、电子扫描显微镜（scanning electron microscope,SEM）观察了微生物的数量、分布和形态;通过批次试验考察了污泥在厌氧/好氧和厌氧/缺氧2种模式下的释磷和吸磷特征。结果表明：该双污泥系统缺氧池中聚磷菌占总细菌比例的69.7%,明显高于单污泥系统中富集的聚磷菌比例,污泥中的微生物多呈杆状;厌氧/好氧、厌氧/缺氧模式下单位污泥浓度（mixed liquor suspended solids,MLSS）总吸磷量（以PO43--P计）分别为22.84、18.60 mg/g,反硝化聚磷菌（denitrifying polyphosphate-accumulating organisms,DPAO）占聚磷菌（polyphosphate-accumulating organisms,PAO）的比例为81.44%,表明在长期的厌氧/缺氧运行条件下可以富集到以硝酸盐为电子受体的反硝化聚磷菌,同时还存在着仅以氧气为电子受体的聚磷菌;通过pH值和氧化还原电位（oxidation reduction potential,ORP）的实时监测可以快速地了解污水生物处理系统中各类反应的进程,对调控工艺参数有着重要的意义。综上所述,为保证污水生物处理工艺的正常稳定运行,将微生物分析与常规的化学参数分析结合起来考察将是未来发展的必然趋势。     

Microbial contribution to SOM quantity and quality in density fractions of temperate arable soils

The formation of soil organic matter (SOM) very much depends on microbial activity. Even more, latest studies identified microbial necromass itself being a significant source of SOM and found microbial products to initiate and enhance the formation of long-term stabilized SOM. The objectives of this study were to investigate the microbial contribution to SOM in pools of different stability and its impact on SOM quality. Hence, four arable soils of widely differing properties were density-fractionated into free and occluded particulate organic matter (fPOM, oPOM < 1.6 g cm⁻³ and oPOM < 2.0 g cm⁻³) and mineral associated organic matter (MOM > 2.0 g cm⁻³) by using sodium polytungstate. These fractions were characterized by in-source pyrolysis-field ionization mass spectrometry (Py-FIMS). Main SOM compound classes of the fractions were determined and further SOM properties were derived (polydispersity, thermostability). The contribution of microbial derived input to arable soil OM was estimated from the hexose to pentose ratio of the carbohydrates and the ratio of C₄–C₂₆ to C₂₆–C₃₆ fatty acids. Additionally, selected samples were investigated by scanning electron microscopy (SEM) for visualizing structures as indicators for the origin of OM. Results showed that, although the samples differed significantly regarding soil properties, SOM composition was comparable and almost 50% of identifiable SOM compounds of all soils types and all density fractions were assigned to phenols, lignin monomers and alkylaromatics. Most distinguishing were the high contents of carbohydrates for the MOM and of lipids for the POM fractions. Qualitative features such as polydispersity or thermostability were not in general assignable to specific compounds, density fractions or different mean residence times. Only the microbial derived part of the soil carbohydrates could be shown to be correlated with high SOM thermostability (r² = 0.63**, n = 39). Microbial derived carbohydrates and fatty acids were both enriched in the MOM, showing that the relative contribution of microbial versus plant-derived input to arable SOM increased with density and therefore especially increased MOM thermostability. Nevertheless, the general microbial contribution to arable SOM is suggested to be high for all density fractions; a mean proportion of about 1:1 was estimated for carbohydrates. Despite biomolecules released from living microorganisms, SEM revealed that microbial mass (biomass and necromass) is a considerable source for stable SOM which is also increasing with density.     

Determination of ammonium n and nitrate n in acid permanganate solution used to absorb ammonia,nitric oxide,and nitrogen dioxide evolved from soils

Abstract

Simple steam distillation methods are described for determination of ammonium N and nitrate N in acid KMnO₄ solution used to absorb NH₃, NO and NO₂ evolved from soils. They involve use of MgO for distillation of ammonia and of FeSO₄, Ag₂SO₄, and MgO for reduction of nitrate to ammonia. The methods are rapid and precise, and they permit nitrogen‐15 analysis of NH₃‐N and (NO + NO₂)‐N evolved from soils.     

Phospholipid fatty acid composition of a 2,4,6-trinitrotolune contaminated soil and an uncontaminated soil as affected by a humification remediation process

Analysis of phospholipid fatty acids (PLFAs) was performed to investigate effects of 2,4,6-trinitrotoluene (TNT) contamination and soil remediation on microbial biomass and community structure. A TNT-contaminated and an uncontaminated soil from a former ammunition plant were analysed before and after a humification/remediation process. TNT contamination reduced microbial biomass but indicated only minor differences in PLFA composition between the contaminated and uncontaminated soils. The humification process increased microbial biomass and altered soil PLFA patterns to a larger degree than did TNT contamination.     

Microbial community structure and function: The effect of silvicultural burning and topographic variability in northern Alberta

Forest floor chemistry and microbial communities can be influenced by forest land management, such as harvesting and prescribed burning. Here, we used phospholipid fatty acid (PLFA) and multiple carbon-source substrate-induced respiration (MSIR) analyses to characterize microbial communities of deciduous, mixedwood and coniferous boreal forest floors with different silvicultural treatments. The sites were stem-only harvested with 10% retention, and silvicultural treatments consisting of slash being evenly distributed on the site and then burned, or not burned. The burned sites exhibited lower microbial biomass and greater NO₃⁻ concentrations than the unburned sites. However, burning appeared to have no effect on forest floor microbial community structure or function. On the other hand, during drier months (August sampling), the composition of forest floor microbial communities appeared to be strongly influenced by topographic position rather than stand related differences. Harvested sites located at higher elevations had similar microbial communities, regardless of the overstory composition, while coniferous and mixedwood sites located at lower elevations had similarly structured microbial communities that were distinct from deciduous sites. Differences in microclimatic conditions of the forest floor between higher elevation sites and lower elevations sites may select for some microbial groups over others. Indicator analysis found a strong association of a fungal PLFA biomarker (20:1ω9c), with sites at higher elevation, while a biomarker for actinomycetes (10Me19:0) was strongly associated with deciduous sites at lower elevation. Structural differences in microbial communities observed between sites at higher and lower elevations appear to be linked to seasonal patterns in moisture, as previous studies in this region found no apparent effect of elevation during times of higher monthly precipitation.