Mercury speciation by X-ray absorption fine structure spectroscopy and sequential chemical extractions: a comparison of speciation methods

Determining the chemical speciation of mercury in contaminated mining and industrial environments is essential for predicting its solubility, transport behavior, and potential bioavailability as well as for designing effective remediation strategies. In this study, two techniques for determining Hg speciation--X-ray absorption fine structure (XAFS) spectroscopy and sequential chemical extractions (SCE)--are independently applied to a set of samples with Hg concentrations ranging from 132 to 7539 mg/kg to determine if the two techniques provide comparable Hg speciation results. Generally, the proportions of insoluble HgS (cinnabar, metacinnabar) and HgSe identified by XAFS correlate well with the proportion of Hg removed in the aqua regia extraction demonstrated to remove HgS and HgSe. Statistically significant (>10%) differences are observed however in samples containing more soluble Hg-containing phases (HgCl2, HgO, Hg3S2O4). Such differences may be related to matrix, particle size, or crystallinity effects, which could affect the apparent solubility of Hg phases present. In more highly concentrated samples, microscopy techniques can help characterize the Hg-bearing species in complex multiphase natural samples.     

X-ray absorption and micro X-ray fluorescence spectroscopy investigation of copper and zinc speciation in biosolids

Despite its pivotal role in determining the risks and time frames associated with contaminant release, metal speciation remains a poorly understood aspect of biosolids chemistry. The work reported here used synchrotron-based spectroscopy techniques to investigate the speciation of copper and zinc in a range of Australian biosolids. High resolution element mapping of biosolids samples using micro X-ray fluorescence spectroscopy revealed considerable heterogeneity in key element associations, and a combination of both organic and inorganic copper and zinc binding environments. Linear combination fitting of K-edge X-ray absorption spectra indicated consistent differences in metal speciation between freshly produced and stockpiled biosolids. While sulfide minerals play a dominant role in metal binding in freshly dewatered biosolids, they are of lesser importance in dried biosolids that have been stockpiled. A degree of metal binding with iron oxide minerals was apparent but the results did not support the hypothesis that biosolids metals are chiefly associated with iron minerals. This work has potential implications for the long-term stability of metals in biosolids and their eventual fate following land application.     

Molybdenum speciation in uranium mine tailings using X-ray absorption spectroscopy

Uranium (U) mill tailings in northern Saskatchewan, Canada, contain elevated concentrations of molybdenum (Mo). The potential for long-term (>10,000 years) mobilization of Mo from the tailings management facilities to regional groundwater systems is an environmental concern. To assist in characterizing long-term stability, X-ray absorption spectroscopy was used to define the chemical (redox and molecular) speciation of Mo in tailings samples from the Deilmann Tailings Management Facility (DTMF) at the Key Lake operations of Cameco Corporation. Comparison of Mo K near-edge X-ray absorption spectra of tailings samples and reference compounds of known oxidation states indicates Mo exists mainly as molybdate (+6 oxidation state). Principal component analysis of tailings samples spectra followed by linear combination fitting using spectra of reference compounds indicates that various proportions of NiMoO(4) and CaMoO(4) complexes, as well as molybdate adsorbed onto ferrihydrite, are the Mo species present in the U mine tailings. Tailings samples with low Fe/Mo (<708) and high Ni/Mo (>113) molar ratios are dominated by NiMoO(4), whereas those with high Fe/Mo (>708) and low Ni/Mo (<113) molar ratios are dominated by molybdate adsorbed onto ferrihydrite. This suggests that the speciation of Mo in the tailings is dependent in part on the chemistry of the original ore.     

Examination of arsenic speciation in sulfidic solutions using X-ray absorption spectroscopy

Both thioarsenites and thioarsenates have been demonstrated to exist in sulfidic waters, yet there is uncertainty regarding the geochemical conditions that govern the formation of these arsenic species. The purpose of this research was to use advanced spectroscopy techniques, speciation modeling, and chromatography to elucidate the chemical speciation of arsenic in sulfidic solutions initially containing arsenite and sulfide. Results of X-ray absorption spectroscopy (XAS) show that experimental solutions contained mixtures of arsenite and thioarsenites with increasing substitution of sulfur for oxygen on arsenic as the sulfide concentration increased. Experimental samples showed no evidence of polymeric arsenic species, or transformation of thioarsenites to thioarsenates. The arsenic speciation measured using XAS was similar to predictions obtained from a thermodynamic model for arsenic speciation, excluding thioarsenate species in sulfidic systems. Our data cast some doubt on the application of chromatographic methods for determining thioarsenates and thioarsenites (or mixtures) in natural waters in cases where the arsenic oxidation state cannot be independently verified. The same chromatographic peak positions proposed for thioarsenates can be explained bythioarsenite species. Furthermore, sample dilution was shown to change the species distribution and care should be taken to avoid sample dilution prior to chromatographic analysis.     

Combined speciation analysis by X-ray absorption near-edge structure spectroscopy, ion chromatography, and solid-phase microextraction gas chromatography-mass spectrometry to evaluate biotreatment of concentrated selenium wastewaters

In this study we evaluate the potential of anaerobic granular sludge as an inoculum for the bioremediation of selenium-contaminated waters using species-specific analytical methods. Solid species formed by microbial reduction were investigated using X-ray absorption near-edge structure (XANES) spectroscopy at the selenium K-edge. Furthermore, dissolved selenium species were specifically determined by ion chromatography (IC) and solid-phase microextraction gas chromatography-mass spectrometry (SPME-GC-MS). Least-squares linear combination of the XANES spectra for samples incubated with the highest selenate/selenite concentrations (10(-3) M) show the predominance of elemental selenium and a Se(-I) selenide, such as ferroselite, the thermodynamically most stable iron selenide. In contrast, elemental selenium and Se(-II) selenides are the main species detected at the lower selenate/selenite concentrations. In each repeated fed batch incubation, most aqueous selenite anions were converted into solid selenium species, regardless of the type of electron donor used (acetate or H(2)/CO(2)) and the selenium concentration applied. On the other hand, at higher concentrations of selenate (10(-4) and 10(-3) M), significant amounts of the oxyanion remained unconverted after consecutive incubations. SPME-GC-MS demonstrated selenium alkylation with both electron donors investigated, as dimethyl selenide (DMSe) and dimethyl diselenide (DMDSe). Selenite was even more alkylated in the presence of H(2)/CO(2) (maximum 2156 μg of Se/L of DMSe + DMDSe) as compared to acetate (maximum 50 μg of Se/L). In contrast, selenate was less alkylated using both electron donors (maximum 166 and 3 μg of Se/L, respectively). The high alkylation potential for selenite limits its bioremediation in selenium laden waters involving H(2)/CO(2) as the electron donor despite the fact that nontoxic elemental selenium and thermodynamically stable metal selenide species are formed.     

Arsenic speciation analysis of cultivated white button mushrooms (Agaricus bisporus) using high-performance liquid chromatography-inductively coupled plasma mass spectrometry, and X-ray absorption spectroscopy

Agaricus bisporus mushrooms were grown in compost amended with either arsenic-contaminated mine waste or an arsenate solution, to a final concentration of approximately 200 microg g(-1). Fungi were cultivated at a small-scale mushroom facility in Vineland (ON), where the controlled environment allowed for a large number of fruiting bodies (mushrooms) to be produced. The total arsenic concentrations as well as speciation were examined for each treatment over several harvests (breaks). Total concentrations were determined by acid digestion and inductively coupled plasma mass spectrometry (ICP-MS) detection and ranged from 2.3 to 16 microg g(-1) dry mass in treatment mushrooms. Arsenic compounds were extracted from mushrooms with methanol/water (1:1 v/v), and separated by high-performance liquid chromatography (HPLC, anion/cation exchange) before detection with ICP-MS. Fruiting bodies from all treatments contained arsenite, dimethylarsinic acid (DMA), and arsenobetaine (AB), and to a lesser extent arsenate and trimethylarsine oxide (TMAO). The ratio of arsenic compounds did not vary greatly over the first three harvests. AB was absent in compost not inoculated with A. bisporus supporting the hypothesis that AB is a product of fungal, not microbial, arsenic metabolism. X-ray absorption spectroscopy results lead us to hypothesize that AB plays a role in nutrient translocation within the fruiting body, as well as maintaining turgor pressure to ensure the mushroom cap remains elevated for maximum spore dispersal.     

近红外光谱结合主成分分析和灰色关联分析的苦荞产地溯源

为实现苦荞产地溯源以及确定苦荞成分对苦荞产地溯源的影响程度,对朔州、内蒙古、云贵高原、四川大凉山、陕西5个产地的72个苦荞样本的近红外光谱数据进行了主成分分析(principal component analysis,PCA)和灰色关联分析。结果表明,PCA可以很好地实现不同产地苦荞的聚类,得到的特征波长分别为1 370、1 680、870和971 nm;将上述特征波长与苦荞的6种成分进行灰色关联分析,其灰色关联度由大到小排列为:碳水化合物>蛋白质>脂肪>钠>硒>黄酮;依据关联度大小,从官能团层面确定了碳水化合物和蛋白质是对苦荞产地溯源影响最大的两个成分。表明PCA和灰色关联分析结合近红外光谱技术可以实现苦荞产地溯源研究,为苦荞地理标志产品鉴别提供了一种快速、高效、低成本的方法。     

Spatial distribution and speciation of lead around corroding bullets in a shooting range soil studied by micro-X-ray fluorescence and absorption spectroscopy

We investigated the spatial distribution and speciation of Pb in the weathering crust and soil surrounding corroding metallic Pb bullets in a shooting range soil. The soil had a neutral pH, loamy texture, and was highly contaminated with Pb, with total Pb concentrations in the surface soil up to 68 000 mg kg(-1). Undisturbed soil samples containing corroding bullets were collected and embedded in resin, and polished sections were prepared for micro-X-ray fluorescence (micro-XRF) elemental mapping and micro-X-ray absorption near edge structure (micro-XANES) spectroscopy. Bullet weathering crust material was separated from the metallic Pb cores and analyzed by powder X-ray diffraction analysis. Our results show a steep decrease in total Pb concentrations from the bullet weathering crust into the surrounding soil matrix. The weathering crust consisted of a mixture of litharge [alpha-PbO], hydrocerussite [Pb3(CO3)2-(OH)2], and cerussite [PbCO3], with litharge dominating near the metallic Pb core and cerussite dominating in the outer crust, which is in contact with the soil matrix. On the basis of these results and thermodynamic considerations, we propose that the transition of Pb species after oxidation of Pb(O) to Pb(II) follows the sequence litharge --> hydrocerussite --> cerussite. Consequently, the solubility of cerussite limits the activity of Pb2+ in the soil solution in contact with weathering bullets to < or =1.28 x 10(-6) at pH 7, assuming that the CO2 partial pressure (PCO2) in the soil is equal or larger than in the atmosphere (PCO2 > or = 0.000 35 atm).     

Arsenic speciation and phytoavailability in contaminated soils using a sequential extraction procedure and XANES spectroscopy

In this study, a sequential extraction procedure (SEP) and X-ray absorption near edge structure (XANES) spectroscopy were used to determine the solid-phase speciation and phytoavailability of arsenic (As) of historically contaminated soils from As containing pesticides and herbicides and soils spiked with As in the laboratory. Brassica juncea was grown in the contaminated soils to measure plant available As in a glasshouse experiment. Arsenic associated with amorphous Fe oxides was found to be the dominant phase using both SEP and XANES spectroscopy. Arsenic predominantly existed in arsenate (As(V)) form in the soils; in a few samples As was also present in arsenite (As(III)) form or in scorodite mineral. Arsenic concentration in shoots showed significant (p < 0.001-0.05) correlations with the exchangeable As (r = 0.85), and amorphous Fe oxides associated As evaluated by the SEP (r = 0.67), and As associated with amorphous Fe oxides as determined by XANES spectroscopy (r = 0.51). The results show that As in both fractions was readily available for plant uptake and may pose a potential risk to the environment. The combination of SEP and XANES spectroscopy allowed us the quantitative speciation of As in the contaminated soils and the identification of valence and mineral forms of As. Such detailed knowledge on As speciation and availability is vital for management and rehabilitation of As-contaminated soils.     

Speciation of zinc in municipal solid waste incineration fly ash after heat treatment: an X-ray absorption spectroscopy study

Fly ash is commonly deposited in special landfills as it contains toxic concentrations of heavy metals, such as Zn, Pb, Cd, and Cu. This study was inspired by our efforts to detoxify fly ash from municipal solid waste incineration by thermal treatment to produce secondary raw materials suited for reprocessing. The potential of the thermal treatment was studied by monitoring the evaporation rate of zinc from a certified fly ash (BCR176) during heating between 300 and 950 degrees C under different carrier gas compositions. Samples were quenched at different temperatures for subsequent investigation with X-ray absorption spectroscopy (XAS). The XAS spectra were analyzed using principal component analysis (PCA), target transformation (TT), and linear combination fitting (LCF) to analyze the major Zn compounds in the fly ash as a function of the temperature. The original fly ash comprised about 60% zinc oxides mainly in the form of hydrozincite (Zn5(OH)6(CO3)2) and 40% inerts like willemite (Zn2SiO4) and gahnite (ZnAl2O4) in a weight ratio of about 3:1. At intermediate temperatures (550-750 degrees C) the speciation underlines the competition between indigenous S and Cl with solid zinc oxides to form either volatile ZnCl2 or solid ZnS. ZnS then transformed into volatile species at about 200 degrees C higher temperatures. The inhibiting influence of S was found absent when oxygen was introduced to the inert carrier gas stream or chloride-donating alkali salt was added to the fly ash.     

Real-time X-ray absorption spectroscopy of uranium, iron, and manganese in contaminated sediments during bioreduction

The oxidation status of uranium in sediments is important because the solubility of this toxic and radioactive element is much greater for U(VI) than for U(IV) species. Thus, redox manipulation to promote precipitation of UO2 is receiving interest as a method to remediate U-contaminated sediments. Presence of Fe and Mn oxides in sediments at much higher concentrations than U requires an understanding of their redox status as well. This study was conducted to determine changes in oxidation states of U, Fe, and Mn in U-contaminated sediments from Oak Ridge National Laboratory. Oxidation states of these elements were measured in real-time and nondestructively using X-ray absorption spectroscopy on sediment columns supplied with synthetic groundwater containing organic carbon (OC, 0, 3, 10, 30, and 100 mM OC as lactate) for over 400 days. In sediments supplied with OC > or = 30 mM, 80% of the U was reduced to U(IV), with transient reoxidation at about 150 days. Mn(III,IV) oxides were completely reduced to Mn(II) in sediments infused with OC > or = 3 mM. However, Fe remained largely unreduced in all sediment columns, showing that Fe(III) can persist as an electron acceptor in reducing sediments over long times. This result in combination with the complete reduction of all other potential electron acceptors supports the hypothesis that the reactive Fe(III) fraction was responsible for reoxidizing U(IV).     

SERS结合PCA-LDA分析鉴别鸡肉中硝基呋喃类代谢物的混合残留

以纳米Au溶胶和NaCl溶液为活性增强基底,对鸡肉中残留的两种呋喃它酮代谢物(AMOZ)和呋喃妥因代谢物(AHD)进行表面增强拉曼光谱(SERS)快速检测技术研究。采用自适应迭代惩罚最小二乘法消除原始数据中的背景干扰,应用标准归一化进行光谱预处理,并结合主成分—线性判别方法(PCA-LDA)建立识别模型,得出模型校正集的判别正确率为90.48%,预测集的判别正确率为94.29%。研究表明,SERS技术与PCA-LDA相结合可以有效地鉴别出鸡肉样本中残留的AMOZ和AHD。     

应用主成分和判别分析的红外光谱法快速鉴别酸败植物油

通过收集并分析40个合格植物油和44个酸败植物油的傅里叶变换红外光谱,选取25个合格植物油和39个酸败植物油组成训练集,利用主成分分析获得累积可信度95%的三个主成分及对应的1743¹710cm-1、1172¹130cm-1、2945²844cm-1、1728¹689cm-1、2987²840cm-1和1731¹660cm-1对植物油酸败最为敏感的光谱波数范围。在主成分分析的基础上,选取对植物油酸败敏感的波段,利用训练集建立鉴别植物油酸败判别分析模型。采用验证集20个样品验证判别分析模型,判别正确率达100%。主成分结合判别分析的红外光谱法能快速、准确、无损地区分合格植物油和酸败植物油。      

Genetic parameter estimates for body conformation traits using composite index,principal component,and factor analysis

Information about genetic parameters is population specific and it is crucial for designing animal breeding programs and predicting response to selection. This study was carried out to estimate the genetic parameters for 23 body conformation traits of 45,517 Chinese Holstein reared in Eastern China from 1995 to 2017 with the Bayesian inference method using a linear animal mixed model. The methods to integrate these traits included (1) using the composite index from the Dairy Association of China and (2) applying principal component analysis and factor analysis to explore the relationship between the conformation traits. Estimates of heritability using the composite index were low (0.04; feet and legs) to moderate (0.23; body capacity). Strong genetic correlations were observed between the individual body conformation traits. Both principal components (1 to 7; eigenvalues ≥ 1) and latent factors (1 to 7; eigenvalues ≥ 1) explained 60.37% of total variability. Principal component 1 and factor 1 accounted for the traits that are usually associated with milk production. Moderate to low heritability were estimated through multi-trait analysis for principal components (from 0.07 to 0.21) and latent factors (from 0.07 to 0.23). Genetic correlations among the 2 multivariate techniques are typically lower compared with the one existing among the measured traits. Results from these analyses suggest the possibility of using both principal component analysis and factor analysis in morphological evaluation, simplifying the information given by the body conformation traits into new variables that could be useful for the genetic improvement of the Chinese Holstein population. This information could also be used to avoid analyzing large number of correlated traits, thereby improving precision and reducing computation burdens to analyze large and complex data.     

主成分分析和聚类分析法研究刺玫果黄酮类成分HPLC指纹图谱

采用高效液相色谱法研究了30批不同品种、不同产地的刺玫果黄酮类成分指纹图谱,并进行主成分分析和聚类分析。采用Athena-C18色谱柱,流动相乙腈-0.1%（v/v）磷酸水溶液,梯度洗脱,流速1.0 mL/min,检测波长360 nm,建立刺玫果指纹图谱。结果表明,30批刺玫果相似度在0.772⁰.995之间,其中22批黄刺玫果相似度均大于0.958,相对保留时间RSD小于1.0%,通过共有模式筛选出15个共有特征峰,其中指认3个共有峰,分别为芦丁、金丝桃苷和槲皮素;方法的精密度、重复性和稳定性的峰面积RSD分别小于2.9%、4.1%和4.9%,芦丁、金丝桃苷和槲皮素的加样回收率分别为97.3%±1.2%,96.2%±1.9%和98.2%±1.1%,RSD分别为3.2%、2.4%和2.6%,符合指纹图谱的检测要求;运用SPSS 22.0软件进行主成分分析和聚类分析,结果主成分分析将样品分为2大类,2个主成分的累积方差贡献为80.3%,聚类分析分为3类,两种分类方法与相似度评价结果一致。该方法具有良好的精密度、重复性和稳定性,结合相似度评价、主成分分析和聚类分析3种方法,可以快速鉴别不同种类的刺玫果,并为有效控制刺玫果的质量提供方法。      

主成分和判别分析在清香型白酒产地溯源中的应用

采用气相色谱法分析不同产地清香型白酒中乙酸乙酯、乳酸乙酯、乙酸等12种主体香味成分的含量,利用SPSS22.0软件对数据进行主成分和判别分析,可以将12个指标提取3个主成分,建立3个判别典型函数。利用建立判别函数可以对5个不同产地的78个白酒样品100%进行正确判别。该方法为不同产地白酒的溯源和真伪鉴别提供一条新的途径。     

Trace elements in faba bean (Vicia fabaL) plant and soil as determined by atomic absorption spectroscopy and ion selective electrode

Trace (Ag, Au, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr and Zn) and macro (Ca, K, Mg and Na) element concentrations were determined by atomic absorption spectrophotometry, and chloride by an ion selective electrode, in different parts of the faba bean (Vicia faba L) plant. Leaf, stem, pod, pericarp, cotyledon, testa and seeds were all analysed as were soil samples taken from the immediate vicinity of the plant roots at depths of 10, 30 and 60 cm before and after planting the bean plant. The experiment was situated on the shores of the High Dam Lake in Aswan (Egypt). The bean leaves showed the highest concentrations of Ca, Mg, Fe, Sr, Mn, Ni, Co, Pb and Cr while the seeds showed the highest concentrations of Zn and Cu. The highest levels of trace elements in the soil were found at 60 cm depth after planting which suggests the uptake of most trace elements by the plant is from the 10–30 cm depth zone. Statistically there were significant correlations between trace element concentrations in the bean and soil samples. The levels of trace elements in the bean under study were not considered to be toxic for man or animal uses. © 1998 SCI.     

Application of principal component analysis to the prediction of lucerne forage protein content and in vitro dry matter digestibility by NIR spectroscopy

Application of principal component regression (PCR) was proposed for the development of a prediction equation of forage composition by near infra-red spectroscopy. PCR involves two steps: (a) the creation of new synthetic variables by principal component analysis (PCA) of spectral data, and (b) multiple linear regression with these new variables. Results obtained by this procedure have been compared with those generated by the conventional application of multiple linear regression (MLR) on spectral data. The comparison used the determination of protein content and in vitro dry matter digestibility (IVDMD) in 345 samples of lucerne forages. For protein determination, results of both procedures were quite similar (correlation coefficients: 0.978 and 0.980; standard errors of calibration: 0.86 and 0.84% DM; standard errors of prediction: 0.81 and 0.80% DM respectively for MLR and PCR prediction equations). The same was observed for IVDMD determination (correlation coefficients: 0.942 and 0.951; standard errors of calibration: 1.89 and 1.71% DM; standard errors of prediction: 2.22 and 2.22% DM, respectively). A large number of PCA variables were necessary for an accurate prediction of both constituents. The influence of the number of regression terms introduced in the PCR equation has been studied. The criterion for stopping the introduction of new terms in PCR did not seem as critical as in MLR.