古人类骨骼中微量元素的分析及其与古代食谱的关联

采用等离子体质谱(ICP-Ms)法对三峡地区及长江下游地区出土的古墓中的人体骨骼中的微量元素Zn、Sr、Ba、Ca进行了分析，并与原子吸收光谱(AAS)对照，结果表明：ICP-MS是骨化学微量元素分析很好的方法，它相对FAAS，具有灵敏度高，检出限低，可快速进行多元素检测等优点，对溶液中元素的检出限可达到ng/L数量级，对元素的高含量和低含量都能进行准确测量。本实验以Zn、Sr、Ba、Ca为指示剂，根据其测量结果，还对上述两地区的古人类食谱进行了初步探讨。     

碳酸钙对去卵巢大鼠骨元素代谢的影响

用测定骨元素含量的方法,分析了碳酸钙(CaCO3)对去卵巢大鼠骨元素代谢的影响。将健康4月龄雌性SD大鼠24只,用抽签法随机分成4组:正常对照组,假去卵巢组,去卵巢组,去卵巢 CaCO3组。去卵巢 CaCO3组大鼠于去卵巢手术后第2 d开始给予CaCO3灌胃,w(Ca)=20mg/kg,1次/d,持续11周。结果表明,去卵巢大鼠骨Ca、S、Mg、Mn等元素含量显著降低,Zn、Co含量降低,骨P含量增加;CaCO3可使去卵巢大鼠降低的骨Ca、S、Mg、Zn、Co、Mn等元素含量显著回升,骨P含量显著回降;CaCO3可纠正去卵巢大鼠的骨元素代谢紊乱。提示补钙防治骨质疏松是通过纠正骨矿物元素代谢紊乱而实现的。     

电感耦合等离子体原子发射光谱法测定白云鄂博富钾板岩中铁、钙、镁、铝和钡的含量

建立了电感耦合等离子体原子发射光谱法(ICP-AES)测定白云鄂博富钾板岩中Fe、Ca、Mg、Al、Ba含量的方法。将0.3 g富钾板岩样品置于镍坩埚中,用2.0 g氢氧化钠和2.0 g过氧化钠于750℃熔解,再加入20 mL盐酸进行酸化,采用ICP-AES测定其中Fe、Ca、Mg、Al、Ba的含量。Fe、Ca、Mg、Al、Ba的最佳分析谱线分别为259.940,396.847,279.553,396.152,493.408 nm。结果表明,Fe、Ca、Mg、Al、Ba的质量浓度在一定范围内与其对应的发射强度呈线性关系,检出限(3s)依次为0.016,0.015,0.002 4,0.016,0.014 mg·L~(-1)。按上述方法测定钾长石标准物质(GBW 03116)和富钾板岩样品中Fe、Ca、Mg、Al、Ba的含量,测定值的相对标准偏差(n=11)为0.45%～7.0%,标准物质的测定值与认定值相符。按标准加入法进行回收试验,回收率为95.2%～100%。     

微波辅助消解-电感耦合等离子体原子发射光谱法(ICP-AES)测定几种血藤中17种元素

建立电感耦合等离子体原子发射光谱法(ICP-AES)测定血藤类中药中K,Ca,Mg,P,Sr,Fe,Mn,Zn,Cu,Co,Cr,Al,Ba,Ni,As,Pb和Cd 17种常量和微量元素含量的分析方法。样品用微波辅助消解,ICP-AES法检测几种血藤中17种元素的含量,方法的检出限为0.000 03~0.009 81μg/mL,加标回收率88.37%~110.00%,相对标准偏差(RSD)均小于5.0%,方法可快速、灵敏、准确测定血藤类中药中多种常量、微量元素的含量。血藤样品中除含有人体必需的常量元素K,Ca,Mg外,还含有Fe,Zn,Mn,Cr,Co等必需的微量元素和其它元素P,Ni,Ba,Al,Sr,Pb,Cd,Ba等。     

微波辅助消解ICP-AES法测定几种血藤中17种元素*

目的 建立电感耦合等离子体发射光谱(ICP-AES)法测定血藤类中药中K、Ca、Mg、P、Sr、Fe、Mn、Zn、Cu 、Co、Cr、Al 、Ba、Ni、As、Pb和Cd17种常量和微量元素含量的测定方法。方法 采用微波辅助消解样品,电感耦合等离子体发射光谱(ICP-AES)法测定几种血藤中17种元素的含量。 结果 该方法的检出限为0.00003~0.00981μg/mL,回收率88.37% ~110. 00%,相对标准偏差( RSD) 均小于5.0%。结论 该方法可快速、灵敏、准确测定血藤类中药中多种常量、微量元素的含量。血藤样品中除含有人体必需的常量元素K、Ca、Mg外,还含有Fe、Zn、Mn、Cr、Co等必需的微量元素和其它元素P、Ni、Ba、Al、Sr、Pb、Cd、Ba等。     

基态和亚稳态的Ca、Ba原子与CIO_2化学发光反应的动态学研究

在束-气装置上的单次碰撞条件下,利用低压直流放电选择性地激发碱土金属到亚稳态,观察了Ca(~1S)、Ca(~1S’~3P)、Ba(~1S)、Ba(~1S,~3D)+ClO_2。反应的化学发光.通过测量化学发光总包光强的空间分布,得到这些反应的总碰撞截面为:Ca(~1S)+ClO_2,97(A~2);Ca(~3P)+ClO_2,138(A~2);Ba(~1S)+ClO_2,136(A);Ba(~3D)+ClO_2,239(A~2),计算机模拟化学发光光谱,发现新生产物MO(M=Ca,Ba)的电子激发态A~1П态的相对振动布居分布是非玻尔兹曼分布的,求出反应Ba(~3D)+ClO_2和Ca(~3P)+ClO_2产生的MClC~П→X~2 ∑~+跃迁的化学发光截面分别为51(A~2)和31(A~2),计算光谱中不同成份的光强,得到了反应产生MO、MCl的产物分支比.最后,讨论了这类反应的机理。     

基态和亚稳态的Ca、Ba原子与ClO2化学发光反应的动态学研究

在束-气装置上的单次碰撞条件下, 利用低压直流放电选择性地激发碱土金属到亚稳态, 观察了Ca(~1S)、Ca(~1S’~3P)、Ba(~1S)、Ba(~1S, ~3D)+ClO_2。反应的化学发光. 通过测量化学发光总包光强的空间分布, 得到这些反应的总碰撞截面为: Ca(~1S)+ClO_2, 0.97 nm; Ca(~3P)+ClO_2, 1.38 nm; Ba(~1S)+ClO_2, 13.6 nm; Ba(~3D)+ClO_2, 2.39 nm, 计算机模拟化学发光光谱, 发现新生产物MO(M=Ca, Ba)的电子激发态A~1П态的相对振动布居分布是非玻尔兹曼分布的, 求出反应Ba(~3D)+ClO_2和Ca(~3P)+ClO_2产生的MClC~П→X~2 ∑~+跃迁的化学发光截面分别为0.51 nm和0.31 nm, 计算光谱中不同成份的光强, 得到了反应产生MO、MCl的产物分支比. 最后, 讨论了这类反应的机理。     

利骨素加强尼尔雌醇防治去卵巢大鼠骨元素代谢紊乱的作用

用测定骨元素含量的方法,分析了尼尔雌醇及联合应用尼尔雌醇和利骨素对去卵巢大鼠骨元素代谢的影响。将健康4月龄雌性SD大鼠32只随机分成4组。A组:假去卵巢组;B组:去卵巢组;C组:去卵巢 CCE3(全量)组;D组:去卵巢 CCE3(半量) 利骨素。结果表明,去卵巢大鼠骨Ca、Mg、S、Mn、Zn等含量显著降低,P含量显著增加。单纯应用CCE3或联合应用CCE3和利骨素均可使去卵巢大鼠降低的骨Ca、Mg、S、Mn、Zn等含量显著回升,P含量显著回降,而后者使去卵巢大鼠降低的骨Ca、Mg、Zn、Co等含量回升的作用优于单纯应用CCE3,说明联合应用CCE3和利骨素对抗去卵巢大鼠骨元素代谢紊乱的作用强于单纯应用CCE3。提示利骨素可加强尼尔雌醇防治去卵巢大鼠骨元素代谢紊乱的作用。     

氟化物对幼年大鼠骨矿物质和血微量元素的影响及其相关性研究

为探讨氟化钠对幼年大鼠血清4种微量元素和骨矿物质含量的影响,以及大鼠骨矿物质和血清微量元素的相关性,将80只2月龄SPF级SO大鼠,雌雄各半,随机分成8组：对照（幼年CS、成年AS）组和用药组（幼年高氟组CHS、幼年低氟组CLS、成年高氟组AHS、成年低氟组ALS、幼年长期高氟组HS、幼年长期低氟组15）。对照组灌胃生理盐水,用药组分别按相应时间给予不同剂量的NaF灌胃,测定了大鼠尺骨和血清中的Ca、P、Fe、Zn含量。结果表明,（1）血清微量元素：①与cs组相比,CHS组和CLS组的磷（P）分别增加100．0％和193．8％（P〈0．05）。②与AS组相比,HS组的Ca、Zn分别下降了20．5％和40．0％,而P则增加了74．0％（P〈0．05）;Ls组的Zn下降了33．3％（P〈0．05）。与HS组比较,CHS组的Ca增加22．3％。③与LS组比较,CLS组的P和Zn明显增加49．2％和28．5％（P〈0．05）。（2）骨矿物质：①与As组相比,HS组的Ca分别下降了23．9％（P〈0．05）,Zn则增加了36．1％（P〈0．05）。②与HS组相比,CHS组的Ca和Fe分别增加了42．3％和36．05％,Zn下降了38．6％（P〈0．05）。（3）骨矿物质和血清微量元素的相关性：骨Ca和血Ca、骨P和血P、骨Zn和血Zn、骨Fe和血Fe的相关系数分别为0．435、0．347、0．136和0．059（P〉0．05）。提示长期使用氟化钠,可以导致幼年大鼠血中微量元素代谢紊乱,骨矿物含量降低,但未确定大鼠骨矿物含量和血微量元素具有相关性。     

分子束技术研究Ba与CHCl~3, CCl~4的反应

本文分别在交叉分子束和分子束-气体条件下, 利用化学发光方法, 研究了Ba(^3D)+CH~2Cl~2, CHCl~3,CCl~4和Ca(^1S~O),Ca(^3P),Ba(^1S～O)Ba(^3D)+CCl~4的反应, 实验得出了Ba(^3D)与CH~2Cl~2, CHCL~3, CCl~4反应时, A^2II,B~2Σ^+态BACl产物的发光截面对反应物碰撞能的依赖关系和反应阈能, 以及Ba(^3D)与CCl~4反应时, 产生电子激发态BaCl产物的光子产率。发现当Ba,Ca被激发到亚稳态时, Ba+CCl~4的反应电子基态BaCl产物的振动激发增加; 而Ca+CCl~4的反应电子基态CaCl产物的转动激发增加. 并针对以上结果进行分析讨论。     

INAA of cortical and trabecular bone samples from animals

Instrumental neutron activation analysis (INAA) was applied to determine Ba, Br, Ca, Cl, Fe, K, Mg, Mn, Na, P, Sr and Zn in bovine and porcine rib bones. Precise results were obtained in analyses of freeze-dried cortical and trabecular bones separately, and also of whole bone ashes. Cortical tissues presented higher concentrations of Ba, Ca, Mg, Mn, Na, P, Sr and Zn than those obtained in trabecular ones. Comparisons were also made between the results obtained for bovine and porcine rib bones. This revised version was published online in August 2006 with corrections to the Cover Date.     

On the possibilities of ICP-AES for analysis of archaeological bones

The possibility of using inductively coupled plasma atomic emission spectrometry (ICP-AES) to determine the elemental composition of archaeological bones elements was evaluated and discussed. The interferences of the major elements (Ca, P, K, Na, Al and Fe) on the microelements (Ba, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr, Zn) were investigated and the appropriate analytical lines were selected. The role of different nebulizers (cross-flow, Babington and Meinhard) on detection limits were investigated. The applicability of the proposed procedure was demonstrated analyzing IAEA-SRM-H-5 (Animal bone); and authentic bone sample dating back to the 4^th century BC. These results were compared to ETAAS and ICP-MS.     

Application of neutron activation analysis to the study of element concentration and exchange in fossil bones

It has long been known that a variety of elements are introduced into voids in the structure of bone during fossilization. Visual examination of the cross-section of many bones in the early stages of fossilization reveal a staining which is most intense near the outer surface. This suggests that concentration gradients must exist for elements entering the bone. To investigate this possibility quantitatively, we have determined elemental concentrations in such bones as a function of depth below the outer surface. Using a SLOWPOKE reactor, we have analysed a number of samples of bone taken from secondary deposits of river sediments in the Old Crow region of the Yukon Territory, Canada. Our preliminary work indicates the decrease in concentration with depth into the cortex for previously recognized post-mortal elements such as U, F, Ba, Mn and Fe. Our measurements show that V, Sc, and Co also vary in this way and can be included in this group. As the hollow central shafts of bones are approached, concentrations increase again. Bones found in the Old Crow region display a variety of surface staining ranging from almost white through red to brown and black. There is a strong correlation between Fe and less positive relations between F and Ba, and staining. Highest Mn concentrations occur at the surfaces of light-coloured bones in which the staining is restricted to the outer 1 mm. Because of the wide range of concentrations which exist amont post-mortal elements in these bones, correlations among these elements can be studied. Manganese and barium, for example, are correlated within each bone, but the correlation patterns differ from bone to bone. These relationships must reflect the nature of the chemical processes associated with the deposition of the elements within the bones. A comparison of these patterns show that some of the bones have been exposed to more than one set of environmental conditions. This data thus provides a way of studying these processes in bones in which the introduction of elements from the environment has not completely and uniformly filled all the available voids.     

Are archaeological bones similar to modern bones? An INAA assessment

For more than a decade, archaeometrists have been analyzing archaeologically recovered human bones in an attempt to relate their trace element contents to diet. Although the problems of diagenesis have been recognized, the variable effects have been difficult to establish. In this paper, an assessment is made of the analytical reliability of the INAA determination of major and trace elements, using their short-lived radioisotopes in both regular and defatted modern cancellous bone, and in modern cortical bone. This modern bone information is then compared with analytical data for bones from Egyptian mummies ranging in age from 2000 to 3700 BP, and with normallyburied 11 th century French bones. Diagenetic effects may readily be detected by the measurement of elevated quantities of V, Mn, and Al in soil-contaminated bones. The Ca to P concentration ratios and the organic content may also be used to separate bone from diagenetically altered archaeological specimens.     

Neutron activation analysis of Ca, Cl, Mg, Na, and P content in human bone affected by osteomyelitis or osteogenic sarcoma

The Ca, Cl, Mg, Na, and P content and Ca/P, Ca/Mg, Ca/Na, Cl/Ca, and Cl/Na ratios in samples of intact cortical bone, inflamed bone and osteogenic sarcoma tissue were investigated by neutron activation analysis with high resolution spectrometry of short-lived radionuclides. In osteogenic sarcoma tissue the mass fractions of Cl and Na are higher and the mass fraction of Ca is lower than that of both normal and inflamed bone tissues. It was shown that the differences between the Cl/Ca ratio can be used as an additional test for differential diagnosis between normal or inflamed bone and osteogenic sarcoma.     

Distribution of uranium in human bones

Uranium and calcium contents in human bones (skull, rib and femur) were determined by the fission track method and the inductively coupled plasma-atomic emission spectroscopic method (ICP-AES), respectively. The U/Ca concentration ratio in the bones was found to decrease in the order of rib greater than femur greater than skull, which is in accordance with the decreasing order of the mean annual replacement percentage of bone components. Several femur bones were cut into several longitudinal segments, and uranium and calcium contents in each segment were determined. Among these, the U/Ca ratio in the epiphysis was higher than those in the diaphysis.     

Coal analysis by means of neutron-, gamma activation analysis and X-ray techniques

The elemental concentration of C, Ca, Fe, Sr, Si, S were determined for 5 borehole brown coal samples by means of NAA, PAA and X-ray techniques. The correlation function between carbon content and the heat values and also between Si, Fe, Ca and Sr contents and ash content are discussed.     

On the possibilities of inductively coupled plasma mass spectrometry for analysis of archaeological bones for reconstruction of paleodiet

The possibilities of inductively coupled plasma atomic mass spectrometry for determination of elemental composition of archaeological bones for reconstruction of paleodiet are discussed. The interferences of different polyatomic ions on the determination of Fe, Cu, Mg, Mn, Zn, and Zr are investigated and evaluated. Thus, a method for the determination of Al, As, Ba, Mg, Pb, Sr, V, Zn, and Zr is proposed and is validated by analysis of IAEA-SRM-H-5 (animal bone). The applicability of the proposed procedure is demonstrated analyzing real archaeological bone samples dated to 4th century b.c. and the results are compared with the data obtained by inductively coupled plasma atomic emission spectrometry.     

Particulate matter (PM10) from São Carlos-SP (Brazil): spectroanalytical techniques to evaluate and determine chemical elements

Chemical composition of PM10 was studied during the period of 2014–2015 in the city of São Carlos, Brazil (‘Dos Voluntários’ Square). PM10 samples were directly analysed by wavelength dispersive X-ray fluorescence – WD-XRF (Al, Ca, Ce, Cl, Fe, K, Mg, P, S, Si, Ti, V, and Zn), and by laser-induced breakdown spectroscopy – LIBS (Ba, Ca, Fe, K, Mg, Na, Si and Ti) both for qualitative purposes. For quantitative analysis of Al, Ba, Ca, Fe, K, Na, S, and Zn, the analytes were extracted from samples of PM10 collected, in filters of glass fibre, with an extractive acid solution (HNO₃ and HCl) and determined by inductively coupled plasma optical emission spectrometry – ICP OES. Spatial variations of elemental concentrations (ng m^–3) were significantly higher in winter Al (19.0), Ba (13.6), Ca (20.0), Na (27.0), S (37.1), and Zn (9.5), autumn showed the highest concentration of Na (26.4), spring showed the highest concentration of Fe (11.6), K (13.1) and also S (25.3) and summer did not show a high concentration in the comparison between the seasons at the site. Using principal component analysis (PCA), as a data interpretation tool, with the data obtained by the WD-XRF and LIBS it was not possible to obtain a good correlation, but with the data of ICP OES, it was possible to verify correlations between identified and determinate elements, with samples collected in the autumn, winter, spring and summer seasons in the city of São Carlos. These associated analytical techniques were excellent tools in environmental monitoring, through the analysis of PM10 samples, presenting reliable and efficiency strategy, and based on the PCA and the EF equation was possible to draw the profile of the possible origins of these elements in the city.     

137Cs,trace and toxic elements distribution in Austrian mushrooms

Various mushroom species have been analyzed for their elemental composition (i.e., Al, B, Ba, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, P, Sr and Zn) by means of ICP-AES. The accuracy of the measurements was confirmed by analyzing a series of the same samples by short time activation analysis. The data were evaluated statistically including the values of¹³⁷Cs. The results denote that the distribution of these elements and their correlation of these elements and their correlation coefficients are highly distinctive for each mushroom species. K, Na and P were found to correlate negatively with¹³⁷Cs in most species. Suillus grevillei and Cantharellus cibarius show high Be values (0.27 and 0.30 g g^–1, respectively), while Pb was high in Suillus grevillei (16.3 g g^–1) and Amanita rubescens (9.3 g g^–1). Higher levels of Cd were found in Rozites caperata and Russula vesca with a mean of 9.2 and 16.1 g g^–1, respectively. Cluster analysis was applied to classify these samples according to their botanical species using their elemental composition. The concentrations of Al, Cr, Mn, Na and¹³⁷Cs have no influence on the classification of these samples.