地质样品中贵金属元素的预处理方法研究进展

本文评述了近年来地质样品中贵金属元素分析预处理技术的研究现状和应用进展,对样品分解过程中常用的火试金法、碱熔融法、酸分解法以及样品分离富集过程中的吸附法、碲共沉淀法、离子交换法、溶剂萃取法、蒸馏法、生物吸附法等手段进行了归纳总结,分析了各方法的特点与不足,展望了技术方法未来发展方向。分解方法中的火试金法经分析工作者不断探索及改进,已成为分解贵金属的最佳手段,但其仍存在试剂消耗量大、成本高、流程长等缺点;碱熔融法虽可分解几乎所有地质样品,但其处理后的溶液存在大量钠盐,需经进一步的纯化;酸分解法主要以高压密闭和卡洛斯管的消解方式为主,但受到样品性质的制约。而不同分离富集的手段都具有较强的针对性,如:吸附法多用于Au、Pt、Pd的富集,蒸馏法仅适用于Os、Ru的分析。由于贵金属元素具有颗粒效应强、赋存形式复杂多样以及超痕量等特殊性,需要针对样品的类型特点选择相适应的预处理方法。本文提出,应当在现有的贵金属分解方法基础上,结合当前新的实验设备及实验条件,寻求更加高效、快捷的分解技术,严格控制流程的本底及各个环节的污染问题,实现多技术、多方法联用,满足贵金属分析的要求。     

高压密闭消解技术在土壤有效态样品前处理中的应用

土壤样品经有机酸浸提后,浸提出的溶液中存在大量有机酸及有机质,如未进行破坏处理,进入电感耦合等离子体发射光谱仪(ICP-OES)进样系统后容易堵塞雾化器、中心管、矩管等,或有颗粒黏附于中心管壁和矩管壁上,造成测定结果精密度和准确度差、空白高等问题,进而影响土壤有效态的综合评价。本文将土壤样品用有机酸(DTPA、草酸-草酸铵、柠檬酸等)浸提后,过滤或离心,吸取上清液加入高压密闭消解罐中,经电热板上处理,再加2mL浓硝酸,于180℃烘箱中保温至少3h,采用ICP-OES测定有效态元素铜锌铁锰镉铅镍铬钼硅的含量。本方法采用高压密闭消解技术处理土壤样品,各元素测定结果的相对标准偏差(RSD)为2.5%～5.9%,相对误差为-2.1%～5.2%,回收率为90.1%～103.2%,方法检出限为0.32μg/kg～0.038mg/kg;而采用以往高温炉中灼烧法、硝酸-高氯酸(硫酸)敞开消解法等技术手段,回收率为89.2%～100.5%,方法检出限为0.50μg/kg～0.050mg/kg,两者相比,本方法的测定结果稳定、空白低,分析周期短,适合批量样品的连续分析。     

电感耦合等离子体质谱法测定高锡地质样品中的痕量镉

应用电感耦合等离子体质谱法(ICP-MS)测定地质样品中的痕量镉,存在多种质谱干扰,通常采用在线或离线方程进行校正,当样品中含锡较高时,采用传统固定系数校正方程,易导致测定结果有明显偏离,甚至结果出现负数。本文针对含高锡的地质样品,应用ICP-MS测定其中的镉,采用氢氟酸-高氯酸-硝酸敞开酸溶消解、硝酸浸提体系处理样品,通过测定~(111)Cd、~(113)Cd、~(114)Cd同位素,研究了干扰元素Sn、In、Zr、Mo对镉测定的影响。结果表明镉与干扰源浓度变化呈非简单的正相关性。①同质异位素Sn或In产生的干扰增值Δ(~(114)Cd/~(114)Sn或~(113)Cd/~(113)In)随干扰源浓度增大逐渐变大,~(114)Sn对~(114)Cd的干扰系数在0.0272～0.0222,~(113)In对~(113)Cd的干扰系数在0.0670～0.0412;②Zr和Mo在测定条件下形成氧化物和多原子复合离子物质对Cd均产生不同程度的质谱干扰。通过测定与样品中干扰源浓度相近的单一标准溶液产生的Cd干扰值,经在线修正干扰系数(γ),建立了精确的校正方程。该方法经标准物质验证,准确度高,相对标准偏差在6.57%～9.94%(n=7),方法检出限为0.03mg/kg,达到了地质分析检测要求,为高锡地质样品中的痕量镉分析提供了依据。     

氮限制时间对海绿球藻和微绿球藻生长、总脂含量及脂肪酸组成的影响

本文研究了不同氮限制时间(0、1、2、4、6 d)对海绿球藻(Halochlorococcum sarcotum)和微绿球藻(Nannochloris oculata)叶绿素荧光参数、细胞密度、生物量、叶绿素含量、总脂含量以及脂肪酸组成的影响。本实验结果表明,海绿球藻的最大相对电子传递速率rETR_(max)和快速光曲线的初始斜率α都随氮限制时间增加而降低,而光系统II最大光能转化效率F_v/F_m、非光化学淬灭NPQ以及最小饱和光照强度Ik都有先增加后下降的趋势,各参数都在氮限制第6d达到最小值。微绿球藻上述各参数的变化趋势均为随着氮限制时间增加而逐渐下降。随着氮限制时间增加,海绿球藻和微绿球藻细胞密度都有较小幅度的增加,分别在第5 d和第6 d达到最大值;两种绿藻的叶绿素含量均随氮限制时间的增加而降低,氮限制0 d时叶绿素含量最高, 6 d时叶绿素含量最低;在氮限制第2 d时二者总脂产率都达到最大值,分别为0.021 g·(L·d)~(–1)和0.017 g·(L·d)~(–1),由此可见,适合海绿球藻和微绿球藻产脂的最佳氮限制时间均为2 d。海绿球藻和微绿球藻的脂肪酸主要包括16:0、18:0、20:0、18:1n-9、18:2n-6和16:3n-3等。氮限制对海绿球藻的18:1n-9和MUFA(单不饱和脂肪酸总和)影响显著,均随氮限制时间增加而增加,而PUFA(多不饱和脂肪酸总和)含量随氮限制时间增加而降低;氮限制对微绿球藻的16:0、18:1n-9、16:3n-3、MUFA和PUFA有显著影响,随着氮限制时间增加, 16:0、18:1n-9及MUFA含量逐渐增加,而16:3n-3和PUFA含量逐渐降低。本实验结果可为进一步开发海绿球藻和微绿球藻并对其进行大规模培养提供理论依据。     

舒肝化瘀方联合熊去氧胆酸胶囊治疗原发性胆汁性胆管炎25例临床观察

目的：观察舒肝化瘀方联合熊去氧胆酸胶囊（UDCA）治疗原发性胆汁性胆管炎（PBC）的临床疗效。方法：将50例PBC患者随机分为治疗组和对照组,每组各25例。对照组给予UDCA治疗,治疗组在对照组的基础上联合舒肝化瘀方治疗。2组疗程均为 48 周,观察2组治疗前后的主要症状、体征及肝功能指标、肝纤维化指标和不良反应发生情况。结果：治疗48周后治疗组中医证候总积分得到明显改善,2组中医证候疗效总有效率治疗组为92.00%（23/25）,对照组为84.00%（21/25）,组间比较,差异有统计学意义（P<0.01）。2组肝功能与肝纤维化各项指标均较治疗前明显改善（P<0.01）,且治疗组改善幅度优于对照组（P<0.01）。治疗期间2组均无明显不良反应。结论：舒肝化瘀方联合UDCA治疗PBC抗肝纤维化及改善肝功能疗效显著,安全性好,优于单用UDCA治疗。     

酸洗法测定海洋沉积物有机碳和无机碳含量的致命缺陷

Organic and inorganic carbon contents of marine sediments are important to reconstruct marine productivity,global carbon cycle, and climate change. A proper method to separate and determine organic and inorganic carbons is thus of great necessity. Although the best method is still disputable, the acid leaching method is widely used in many laboratories because of its ease-of-use and high accuracy. The results of the elemental analysis of sediment trap samples reveal that organic and inorganic carbon contents cannot be obtained using the acid leaching method, causing an infinitely amplified error when the carbon content of the decarbonated sample is 12%±1% according to a mathematical derivation. Acid fumigation and gasometric methods are used for comparison, which indicates that other methods can avoid this problem in organic carbon analysis. For the first time, this study uncovers the pitfalls of the acid leaching method, which limits the implication in practical laboratory measurement, and recommends alternative solutions of organic/inorganic carbon determination in marine sediments.     

Eco‐physiological repercussions of dietary arachidonic acid in cell membranes of active tissues of the Gray whale

The radiation of the mammalian land species that became the baleen whales happened about 27–34 Mya. Mammals require omega 6 fatty acids for reproduction. With this long exposure to the omega 3‐rich marine food chain, the Gray whale (Eschrichtius robustus) might be expected to have lost its requirement for omega 6 fatty acids. We report an unexpectedly high content of omega 6 arachidonic acid (ArA) in the Gray whale liver and muscle lipids. This whale migrates 10,000 km from the cold polar, omega 3 oil‐rich food chain to that of the breeding lagoons of the tropical waters. The food web of tropical waters is a source of omega 6 fatty acids, which are hardly present in the cold polar food web. We suggest the reason for this longest of migrations from cold to warm waters is to meet the requirement for omega 6 fatty acids for mammalian reproduction and brain growth. This extreme conservation of omega 6 fatty acids in Gray whale biology has critical implications for mammalian biology and especially for whale conservation.     

Diurnal heterogeneity in silicic acid fluxes in shallow coastal sites: Causes and implications

In shallow coastal areas the amplitude and range of benthic silicic acid fluxes can have a significant influence on benthic–pelagic coupling and the functioning of the pelagic system. To explore the oscillation in fluxes over the diurnal cycle and in particular the influence of microphytobenthos (MPB), an experiment was carried out in a shallow subtidal site in the Bay of Brest (France). Benthic chambers were employed over a 48 h period to measure the variability in silicic acid and oxygen fluxes; MPB migration was investigated using a diving Pulse Amplitude Modulated (PAM) fluorometer and uptake rhythms of silicic acid by natural MPB populations were measured using the ³²Si isotope. It was discovered that silicic acid fluxes fluctuated greatly throughout the diurnal period resulting in an oscillation in the availability of this nutrient for phytoplankton communities. The uptake of silicic acid by the MPB was quantified for the first time and highlighted a 2-fold increase in the demand from night to afternoon periods. The combined silicic acid uptake and the concentration of cells at the sediment–water interface, forming a dense biofilm of MPB, were postulated to be the main processes reducing effluxes at midday. Our work highlighted the many processes which influence silicic acid effluxes in shallow coastal areas and the possible interaction between uptake and dissolution processes. The variations in benthic fluxes over the diurnal period were comparable to observations reported at the seasonal scale. Therefore, up-scaling hourly flux observations to daily and annual estimates should be undertaken with caution. Further we suggest that the main processes influencing flux oscillations over the diurnal period should be considered when planning sampling strategies and extrapolating to larger time scales.     

Dissolved and particulate aluminum in the Columbia River and coastal waters of Oregon and Washington: Behavior in near-field and far-field plumes

The distribution of dissolved (soluble and total) and particulate (leachable and total) aluminum was examined in the Columbia River and estuary, in near-field and far-field river plumes, and in adjacent coastal waters of Washington and Oregon during the River Influence on Shelf Ecosystems (RISE) cruise of May/June 2006. Dissolved and particulate aluminum (Al) concentrations were significantly greater in the river than in the coastal waters that mixed to form the plume. Dissolved Al concentrations in the Columbia River (∼80 nM) were low relative to other major rivers. Leachable and total particulate Al concentrations within the river reached concentrations greater than 1000 nM and 18,000 nM, respectively. Dissolved Al within the Columbia River estuary showed a significant removal (∼60%) at salinities between 0 and 10 with salt-induced flocculation of colloidal Al complexes and enhanced particle scavenging being probable explanations for aluminum removal. Dissolved and particulate Al concentrations were significantly greater in near-field plumes relative to surrounding coastal waters. As the plume advected from near-field to far-field away from the river mouth, dilution of the plume with lower dissolved Al surface waters as well as particle scavenging along the flow path appeared to be controlling dissolved Al distributions. Particle settling as well as dilution with lower particle-load waters led to observed decreases in particulate Al as the plume moved from near-field to far-field. However, the percent-leachable particulate aluminum in both near-field and far-field plumes was remarkably constant at ∼7%. Dissolved and particulate Al in a far-field plume over 100 km southwest of the Columbia River mouth were over an order-of-magnitude greater than surrounding waters, illustrating the importance of the Columbia River plume as a mechanism for transporting Al offshore. Aluminum could be used to trace the input of biologically-required elements such as iron into waters off the shelf.     

Dynamics of particle export on the Northwest Atlantic margin

The Northwest Atlantic margin is characterized by high biological productivity in shelf and slope surface waters. In addition to carbon supply to underlying sediments, the persistent, intermediate depth nepheloid layers emanating from the continental shelves, and bottom nepheloid layers maintained by strong bottom currents associated with the southward flowing Deep Western Boundary Current (DWBC), provide conduits for export of organic carbon over the margin and/or to the interior ocean. As a part of a project to understand dynamics of particulate organic carbon (POC) cycling in this region, we examined the bulk and molecular properties of time-series sediment trap samples obtained at 968 m, 1976 m, and 2938 m depths from a bottom-tethered mooring on the New England slope (water depth, 2988 m). Frequent occurrences of higher fluxes in deep relative to shallower sediment traps and low Δ¹⁴C values of sinking POC together provide strong evidence for significant lateral transport of aged organic matter over the margin. Comparison of biogeochemical properties such as aluminum concentration and flux, and iron concentration between samples intercepted at different depths shows that particles collected by the deepest trap had more complex sources than the shallower ones. These data also suggest that at least two modes of lateral transport exist over the New England margin. Based on radiocarbon mass balance, about 30% (±10%) of sinking POC in all sediment traps is estimated to be derived from lateral transport of resuspended sediment. A strong correlation between Δ¹⁴C values and aluminum concentrations suggests that the aged organic matter is associated with lithogenic particles. Our results suggest that lateral transport of organic matter, particularly that resulting from sediment resuspension, should be considered in addition to vertical supply of organic matter derived from primary production, in order to understand carbon cycling and export over continental margins.