加速溶剂提取/GC-MS同时测定动物组织中有机氯农药和多氯联苯

动物组织样品油脂含量大、干扰杂质多,对其中低含量有机氯农药及多氯联苯的分析会造成较大程度的影响。针对动物组织样品基质复杂的特点,本文以二氯甲烷-丙酮（体积比为1：1）的溶剂体系,采用加速溶剂萃取技术对样品进行提取,在提取过程中尽量减少脂肪的共提出,然后采用凝胶渗透色谱技术去除样品中的大部分油脂,再结合弗罗里硅土为填料的固相萃取方法对样品进一步净化,能够达到充分去除油脂和小分子杂质的目的。采用气相色谱-质谱分析17种有机氯农药及7种指示性多氯联苯,各化合物的回收率在81.6%~113.4%之间,检出限在1.02~3.59 ng/g之间,技术指标优于部分国家标准。本方法改进了动物样品的净化效果,建立了凝胶渗透色谱结合固相萃取技术的净化方法,达到了样品快速自动提取、溶剂用量少、基质净化彻底的目的,降低了方法检出限,能够满足快速、准确检测动物组织中低含量持久性有机污染物的要求。     

电感耦合等离子体发射光谱法测定稀土矿石中15种稀土元素——四种前处理方法的比较

稀土元素在矿石中有多种不同的赋存形式,主要有离子吸附型和矿物晶格型,稀土不同赋存形态对其本身准确分析测定有很大的影响。本文从稀土元素在矿石中不同赋存形态的角度出发,探讨了不同前处理方法对稀土准确测试结果的影响,采用盐酸-硝酸-氢氟酸-高氯酸(四酸)敞开酸溶、盐酸-硝酸-氢氟酸-高氯酸-硫酸(五酸)敞开酸溶、氢氟酸-硝酸封闭压力酸溶、氢氧化钠-过氧化钠碱熔四种方法对离子吸附型和矿物晶格型两类赋存类型的稀土矿石样品进行前处理,电感耦合等离子体发射光谱法测定其中的15种稀土元素。结果表明:对于离子吸附型的稀土矿石标准物质(GBW 07161、GBW 07188),四酸敞开酸溶法测定的结果明显偏低,15种稀土元素大都偏低10%~20%,五酸敞开酸溶法、封闭压力酸溶法和碱熔法的测定值与标准值吻合;而对于稀土以离子化合物及类质同象置换的形式赋存于矿物晶格中的白云鄂博轻稀土矿石样品,三种酸溶法结果较碱熔法均偏低,其中四酸敞开酸溶法偏低最多,约偏低20%左右,五酸敞开酸溶法和封闭压力酸溶法偏低5%~15%。本文提出,对于离子吸附型稀土矿,五酸敞开酸溶法和封闭压力酸溶法可以代替传统操作复杂的碱熔法,但对于稀土以离子形式赋存于矿物晶格型的稀土矿,目前最合适的前处理法是传统的碱熔法。     

电感耦合等离子体发射光谱法测定地球化学样品中的钍

运用电感耦合等离子体发射光谱(ICP-AES)测定地球化学样品中的钍,样品处理方法通常是采用四酸溶矿。但在实际测定中发现,当钍含量接近本底时,检测结果不稳定;当基体干扰大时,钍含量甚至无法检出。本文对样品前处理方法进行改进,采用过氧化钠碱熔样品,10 g/L氢氧化钠溶液过滤洗涤,再用热的40%盐酸溶解沉淀,ICP-AES法测定钍的含量。通过实验确定了钍的最佳分析谱线为401.913 nm,方法检出限为0.21μg/g,精密度(RSD,n=6)为7.7%~15.9%,准确度(n=6)为7.0%~10.0%,加标回收率为92.0%~104.0%。经国家标准物质验证,本方法可准确测定钍含量大于0.21μg/g的样品。方法简便快捷,干扰少,较一般的酸溶ICP-AES测定方法的检出限(0.6~0.7μg/g)低,适用于大批量实际样品的快速检测。     

石英岩化学成分分析标准物质研制

目前巴西、英国、日本、南非等国研制有一些石英岩类标准物质,SiO₂含量均在96%以上,含量范围较窄,定值元素较少。我国尚无石英岩类的标准物质,无法满足石英岩勘查和实际应用的需要。本文研制了3个石英岩化学成分分析标准物质,样品采自我国具有代表性的安徽省凤阳县大庙镇老青山、青海省大通县景阳镇和湖北省蕲春县灵虬山三个石英矿区,利用流化床式气流粉碎机将样品细碎至-45 μm,解决了纯度较高的石英岩粉碎加工易受污染的难题。因石英岩样品难以压制成型,均匀性检验未采用压片制样X射线荧光光谱法,而是采用以电感耦合等离子体发射光谱法和电感耦合等离子体质谱法为主的检验方法。结果表明,方差检验的F值均小于临界值,证明其均匀性符合要求。为期两年的长期稳定性8次检验中未发现统计学意义上的明显变化,在颠震和极端温度条件下所检验的短期稳定性良好。经我国十家实验室使用多种分析方法联合定值,同时探索采用类似元素比较法获取未进行均匀性和稳定性检验的成分的相应不确定度分量,给出了36个成分的认定值(或参考值)和相应的不确定度。3个标准物质现已被批准为国家一级标准物质(编号GBW 07835、GBW 07836、GBW 07837),其主要成分SiO₂的含量相应为92.93%、95.97%、99.18%,呈梯度分布。此系列标准物质具有样品粒度均匀、粒度分布范围窄(D₂₅～D₇₅在4～16 μm之间),定值元素种类多,SiO₂含量分布广泛的特点,可以满足石英岩样品化学成分分析过程中监控的需要。     

Different units of measurement of carotenoids estimation in cotton using hyperspectral indices and partial least square regression

This paper examines the use of canopy reflectance for different units of measurements of carotenoids estimation. Field spectral measurements were collected over cotton in different intensive field campaigns organized during the growing seasons of 2010 and 2011. Three units of measurement were evaluated carotenoids expressed as a mass per unit soil surface area (g/m²), a mass per unit leaf area (μg/cm²), and a mass per unit fresh leaf weight (mg/g), respectively. Four methods were compared to retrieve amount of carotenoids: stepwise multiple linear regression (SMLR), published spectral indices, band combination indices, and partial least square regression (PLSR). Results show that maximum sensitivity of reflectance to variation in different units of measurement of carotenoids was found in the green region at 515–550 nm, and at 715 nm and 750 nm regions in the far-red wavelengths. The predictive accuracies of Car (g/m²), Car (μg/cm²) and Car (mg/g) were tested on a validation data set and the results show that the highest R² values between estimations and observations were 0.468 for Car (g/m²), 0.563 for Car (μg/cm²), and 0.456 for Car (mg/g), with relative root mean square error (RMSE%, RMSE/mean) of 48.72%, 22.07% and 21.07%, respectively. Compared to Car (g/m²) and Car (mg/g), the model performance indices for Car (μg/cm²) show a high degree of consistency among the R² values and RMSE% and MAE% values. Further comparison were performed among the estimation accuracies of different unit carotenoids and among the different approaches used in the study by a paired-t-test. The results indicate that although the best estimation results for Car (μg/cm²) and Car (mg/g) were both obtained based on PLSR, they can be estimated by all four adopted methods without significant differences (P > 0.1). Whereas for Car (g/m²), the best estimation results were obtained based on published vegetation indices CIred-edge, which were significantly better than the estimation results based on SMLR (P < 0.000). In summary, the results of this study show that even the carotenoids expressed on concentration (mg/g) or content (μg/cm²) basis at leaf level can be estimated with the same prediction accuracies to the carotenoids expressed as a mass per unit surface area (g/m²) at canopy level using reflectance measurement at canopy level.     

Compositional mapping of planetary moons by mass spectrometry of dust ejecta

Classical methods to analyze the surface composition of atmosphereless planetary objects from an orbiter are IR and gamma ray spectroscopy and neutron backscatter measurements. The idea to analyze surface properties with an in-situ instrument has been proposed by Johnson et al. (1998). There, it was suggested to analyze Europa's thin atmosphere with an ion and neutral gas spectrometer. Since the atmospheric components are released by sputtering of the moon's surface, they provide a link to surface composition. Here we present an improved, complementary method to analyze rocky or icy dust particles as samples of planetary objects from which they were ejected. Such particles, generated by the ambient meteoroid bombardment that erodes the surface, are naturally present on all atmosphereless moons and planets. The planetary bodies are enshrouded in clouds of ballistic dust particles, which are characteristic samples of their surfaces. In situ mass spectroscopic analysis of these dust particles impacting onto a detector of an orbiting spacecraft reveals their composition. Recent instrumental developments and tests allow the chemical characterization of ice and dust particles encountered at speeds as low as 1 km/s and an accurate reconstruction of their trajectories. Depending on the sampling altitude, a dust trajectory sensor can trace back the origin of each analyzed grain with about 10 km accuracy at the surface. Since the detection rates are of the order of thousand per orbit, a spatially resolved mapping of the surface composition can be achieved. Certain bodies (e.g., Europa) with particularly dense dust clouds, could provide impact statistics that allow for compositional mapping even on single flybys. Dust impact velocities are in general sufficiently high at orbiters about planetary objects with a radius >1000 km and with only a thin or no atmosphere. In this work we focus on the scientific benefit of a dust spectrometer on a spacecraft orbiting Earth's Moon as well as Jupiter's Galilean satellites. This ‘dust spectrometer' approach provides key chemical and isotopic constraints for varying provinces or geological formations on the surfaces, leading to better understanding of the body's geological evolution.     

CSRH光传输线的长度及相位测量

简述CSRH等长光传输线的物理意义,实现等长光传输线的几种方法,通过分析确定了光纤等长精度要求。介绍了两种测量光纤长度的方法,分析计算了CSRH光传输线的相位误差,最后描述了光传输线的相位检测方法。     

膜去溶-电感耦合等离子体质谱法测定环境地质样品中的镉

应用电感耦合等离子体质谱法(ICP-MS)分析环境地质样品中的Cd时,Zr、Mo元素的氧化物和氢氧化物会对Cd造成严重干扰,导致结果有明显的偏差。针对此问题,本文建立了膜去溶-ICP-MS直接测定环境地质样品中微量Cd的分析方法,该方法可有效地消除Zr、Mo氧化物和氢氧化物对Cd的干扰,保证结果准确、可靠。膜去溶-ICP-MS相比于常规ICP-MS测定Cd的方法,可将Zr、Mo氧化物和氢氧化物对Cd的干扰降低到0.001%,检测灵敏度提高3.5倍左右。在给定条件下,Cd的检出限为0.28 ng/L,测定下限为2.2 ng/L,精密度(RSD,n=12)为2.2%。利用该方法分析20种岩石、土壤和沉积物国家标准物质的测定值与标准值相符,表明膜去溶-ICP-MS法直接测定环境地质样品中痕量或超痕量Cd时具有一定的应用潜力。同时,用该方法对2016年中核集团组织的实验室间两个比对样品中的Cd进行测定,稳健Z比分数分别为0.500和-0.964,Z的绝对值都小于2。     

海河流域滹沱河冲洪积扇地下水中农药污染及分布特征

地下水是海河流域滹沱河冲洪积扇重要的饮用水水源,农业种植过程中施用的农药会导致地下水污染,该地区地下水中农药的污染调查工作相对匮乏。为了研究滹沱河冲洪积扇地下水中农药的污染及分布特征,本文利用气相色谱-质谱联用技术分析了30组地下水样品中75种农药组分,用统计学方法对结果进行分析。结果显示:30个采样点中均有农药检出,检测的75种农药中检出40种,有机氯、有机磷、有机氮三类均有检出。检出率最高的为3-羟基呋喃丹(93.3%)、敌杀磷(90.0%)、地茂散(90.0%),30个样品检出浓度之和最大的为呋喃丹(4860.6ng/L)。研究区内三类农药平均检出浓度有机氯(70.8ng/L)有机磷(392.7ng/L)有机氮(580.9ng/L),这主要与三类农药的使用历程和性质相关:有机氯类农药由于其高毒、难降解等特性在1983年被禁用;21世纪初,相对高效、易降解的有机磷类和有机氮类农药应用广泛。三类农药的空间分布特征为从冲洪积扇顶部到中部,农药含量逐渐减少,这主要受冲洪积扇水文地质特征的影响。研究区内HCHs来源为近期林丹使用或HCHs工业降解,DDTs来源为新DDT源的释放或历史上的使用。研究结果可为我国地下水农药的污染监测和地下水相关标准制定提供数据支撑。     

基于BIF条带状铁建造矿化特征的国际铁矿石盈亏平衡运营成本定量研究

国内外铁矿石价格对标基准多采用离岸价或到岸价,而非盈亏平衡运营成本,难以揭示我国铁矿石所面对的真实市场承压价格。为了厘清国际一线生产商的铁矿石盈亏平衡运营成本价格,本文对世界上最重要的条带状铁建造(BIF)矿产地——西澳哈默斯利盆地高品位赤铁矿矿床的矿化特征及代表性铁矿石产品展开系统研究,同时引入巴西铁四角地区的铁英岩型赤铁矿矿石作为对照,分析全球典型高品位赤铁矿矿石经济指标。结合前人研究成果,将西澳哈默斯利盆地与BIF相关的高品位赤铁矿的富集矿化类型划分为假象赤铁矿-针铁矿、微板状赤铁矿与河道沉积型赤铁矿,巴西铁四角主要为铁英岩型赤铁矿。上述各矿化类型对应的铁矿石产品的铁元素含量均高于56%;在杂质元素含量上,假象赤铁矿-针铁矿的磷含量高,微板状赤铁矿的磷、硫含量较高,河道沉积型赤铁矿的磷、硫含量较低,铁英岩型赤铁矿含锰。经定量估算,西澳力拓、必和必拓、FMG和巴西淡水河谷的铁矿石盈亏平衡运营成本价格分别为34.66、36.76、47.35、38.07美元/干吨,可为中国海外权益铁矿项目开发提供运营成本的参考。