Atmospheric and Surface Water Pollution Interpretation in the Gdańsk Beltway Impact Range by the Use of Multivariate Analysis

The present study deals with the application of the hierarchical cluster analysis and non‐parametric tests in order to interpret the Gdańsk Beltway impact range. The data set represents concentration values for major inorganic ions (Na⁺, NH, K⁺, Mg²⁺, Ca²⁺, F⁻, Cl⁻, NO, and SO) as well as electrolytic conductivity and pH measured in various water samples [precipitation, throughfall water, road runoff, and surface water (drainage ditches, surface water reservoirs, and spring water)] collected in the vicinity of the beltway. Several similarity groups were discovered both in the objects and in the variables modes according to the water sample. In the majority of cases clear anthropogenic (fertilizers usage and transport, road salting in winter) and semi‐natural (sea salt aerosols, erosion of construction materials) impacts were discovered. Spatial variation was discovered for road runoff samples and samples collected from surface water reservoirs and springs. Surprisingly no clear seasonal variability was discovered for precipitation chemistry, while some evidences for existing of summer and winter specific chemical profile was discovered for road runoff samples. In general, limited range of the Gdańsk Beltway impact was proven.     

基体差异对电感耦合等离子体质谱法测定过程中Ba氧化物产率的影响及其对Eu测定结果校正的研究

电感耦合等离子体质谱（ICP-MS） 测定地质样品中稀土元素的过程中,尤其对于高Ba基体的地质样品,由Ba形成 的氧化物和氢氧化物离子对Eu元素会产生质谱峰的重叠干扰,严重影响Eu测定结果的准确度和精确度。通过标准溶液的 条件实验,测定Ba干扰项相对Ba总量的比例（干扰率） 并进行相应的Eu扣除,是一种解决干扰导致Eu测定结果偏高的思 路。然而该干扰率在不同基质溶液中是否一致,且随着Ba含量变化是否稳定目前尚不明确。本文通过对不同基体溶液中Ba 对Eu干扰率的测定（低分辨模式测定）,发现随着溶液中Ba浓度的变化,同一基体溶液中该干扰率较为恒定,而不同基体 溶液中干扰率有明显的差别。这说明在对Eu测定结果进行干扰扣除时,需要利用匹配的基体溶液来获取准确的Ba干扰 率。应用这种方法扣除得到的Eu结果与质谱的高分辨模式（R=10000） 下的测定结果较为一致,数据的重现性也较为理 想。因此,利用基体匹配的方式来进行Ba对Eu的数学扣除是一种可行的方法。     

原子荧光光度法测定植物样品中的铋

植物样品经硝酸-高氯酸1次湿法消解后,用氢化物发生-原子荧光光谱法测定铋。测定时加入消泡剂磷酸三丁酯,可有效消除泡沫,降低记忆效应,提高精密度。方法精密度(RSD=12)铋1.50%。经加标回收试验和国家一级标准物质验证,测定结果与标准值吻合。     

快速程序升温-石墨炉原子吸收光谱法测定地质样品中痕量镉

建立了快速程序升温-石墨炉原子吸收光谱测定地质样品中痕量镉的分析方法.样品用硝酸-氢氟酸-高氯酸进行前处理,为提高分析效率,改进了石墨炉升温程序,省去了常规方法中的灰化步骤,使测定镉的程序升温时间由常规的90～100 s降至24 s,工作效率显著提高.方法检出限为0.011 μg/g,加标回收率为93.5%～106.0...     

An Exploration of the Interplay between the Measurement Uncertainty and the Number of Samples in Contaminated Land Investigations

In the assessment of potentially contaminated land, the number of samples and the uncertainty of the measurements (including that from sampling) are both important factors in the planning and implementation of an investigation. Both parameters also effect the interpretation of the measurements produced, and the process of making decisions based upon those measurements. However, despite their importance, previously there has been no method for assessing if an investigation is fit‐for‐purpose with respect to both of these parameters. The Whole Site Optimised Contaminated Land Investigation (WSOCLI) method has been developed to address this issue, and to allow the optimisation of an investigation with respect to both the number of samples and the measurement uncertainty, using an economic loss function. This function was developed to calculate an ‘expectation of (financial) loss’, incorporating costs of the investigation itself, subsequent land remediation, and potential consequential costs. To allow the evaluation of the WSOCLI method a computer program ‘OCLISIM’ has been developed to produce sample data from simulated contaminated land investigations. One advantage of such an approach is that as the ‘true’ contaminant concentrations are created by the program, these values are known, which is not the case in a real contaminated land investigation. This enables direct comparisons between functions of the ‘true’ concentrations and functions of the simulated measurements. A second advantage of simulation for this purpose is that the WSOCLI method can be tested on many different patterns and intensities of contamination. The WSOCLI method performed particularly well at high sampling densities producing expectations of financial loss that approximated to the true costs, which were also calculated by the program. WSOCLI was shown to produce notable trends in the relationship between the overall cost (i.e., expectation of loss) and both the number of samples and the measurement uncertainty, which are: (a) low measurement uncertainty was optimal when the decision threshold was between the mean background and the mean hot spot concentrations. (b) When the hot spot mean concentration is equal to or near the decision threshold, then mid‐range measurement uncertainties were optimal. (c) When the decision threshold exceeds the mean of the hot spot, mid‐range measurement uncertainties were optimal. The trends indicate that the uncertainty may continue to rise if the difference between hot spot mean and the decision threshold increases further. (d) In any of the above scenarios, the optimal measurement uncertainty was lower if there is a large geochemical variance (i.e., heterogeneity) within the hot spot. (e) The optimal number of samples for each scenario was indicated by the WSOCLI method, and was between 50 and 100 for the scenarios considered generally; although there was significant noise in the predictions, which needs to be addressed in future work to allow such conclusions to be clearer.     

混合吸附剂分离富集-电感耦合等离子体质谱法测定地质样品中铂钯金

贵金属分析应用火试金法分离富集时,试金配料复杂、耗时较长,分析成本相对较高,空白较难控制.本文建立了采用过氧化氢-盐酸湿法分解样品,电感耦合等离子体质谱同时测定地质样品中Pt、Pd、Au的分析方法.在10％的盐酸介质中,以LSC-400巯基树脂和活性炭为混合吸附剂,采用动态吸附方式对样品中的Pt、Pd、Au分离富集,用Lu作内标元素,195 Pt、197 Au、108 Pd为待测同位素消除了非谱线干扰和谱线干扰,三元素的回收率均大于96.4％.方法检出限(3σ):Pt为0.06 ng/g,Pd为0.08 ng/g,Au为0.12 ng/g,优于火试金等其他分离富集方法的检出限.应用于测定国家标准物质,Pt、Pd、Au的测定结果与标准值相符,12次测定的相对标准偏差均小于16.1％,满足区域地球化学调查样品的分析要求.该方法操作简便、成本低廉,提高了分析速度,有效地降低了测试过程的空白值.     

植物样品中无机元素分析的样品前处理方法和测定技术

植物样品中无机元素的分析测定在环境地球化学和生物地球化学的研究中起着重要作用。植物样品中元素含量一般较低,须选用科学合理的前处理技术和灵敏度高、精密度好、检出限低的测定方法。本文针对植物样品前处理方法和无机元素分析测定技术的研究进展、优势与不足进行评述。前处理方法主要根据样品和待测元素的性质进行选择:干法灰化所用试剂少、空白值低,但组织致密型的样品不易灰化完全、高温下易造成元素挥发损失;湿法消解样品消解较为完全,但试剂消耗大、空白值高、操作繁琐;微波消解可以防止部分易挥发元素损失,用酸量少、消解速度快,但称样量相对较小,不适于需要大称样量的样品分析。几乎所有针对元素分析的仪器分析技术都可以用于植物样品分析,主要根据仪器适用的元素、必要的干扰校正以及基体改进等方面进行选择:电感耦合等离子体质谱法可同时测定植物样品中40种以上的元素,高分辨质谱的检出限可达fg/mL;电感耦合等离子体发射光谱法适用于某些植物样品中含量较高的P、K、Na等元素的测定;原子吸收光谱法可分析元素达70余种,是普及程度最高的仪器分析技术之一;原子荧光光谱法与氢化物发生技术的联用,在元素含量较低的植物样品分析中技术优势更加明显;新兴的激光诱导击穿光谱技术已被应用于植物样品分析,无需复杂的样品前处理,操作简单快速,可实现原位、在线、实时、多元素同时检测;其他选择性强、灵敏度高的分析技术,满足了一些特定元素不能用常规分析技术测定的需求。当前主流分析技术的样品前处理方法都存在着缺陷,固体进样技术将成为植物样品分析领域的发展方向之一。     

电感耦合等离子体质谱法精确测定地质样品中的微量元素镓

应用电感耦合等离子体质谱法(ICP-MS)对地质样品中微量元素镓进行测试分析时,存在两方面问题:一是不同消解方法各有不足,密闭式消解不能批量处理样品,而敞开式消解过程繁杂;二是质谱测试时需要选择⁶⁹Ga还是⁷¹Ga,确定扣除哪些干扰和相应的扣除系数,这些因素使地质样品中镓元素的测试精度不高。本文基于一般地质样品中有机质含量低的特点,针对ICP-MS分析方法提出:①使用氢氟酸、盐酸、硝酸、高氯酸四种酸混合消解样品,采用半密闭式酸分解法,通过调整加热温度、用酸量、用酸比等加快反应进程,少量的有机质在强酸加热消解时能够反应完全,而不必要进行灰化处理;②采用丰度为39.9%的⁷¹Ga进行测试,使用经验系数0.005,利用⁵⁵Mn¹⁸O对⁷¹Ga位置扣除⁵⁵Mn¹⁶O的干扰。方法精密度在3%以内,方法检出限为0.06 μg/g。本方法简化了样品消解过程,并可批量处理样品,降低了分析成本,在准确测定镓元素的同时还能理想地测定其他微量元素和稀土元素。     

化探中痕量银的测定

对电感耦合等离子体质谱法与一米光栅发射光谱法在化探样品中的痕量银测定进行对比,实验表明,两种方法都具有高精密度和准确度,检出限也符合区域化探的要求,但是在大批量的化探测定及多元素同时测定方面,质谱法操作简单、快速、准确、成本低,优于一米光栅发射光谱法,更适合应用于批量化探样品中银的测定。     

高压力下原状层间错动带三轴不排水剪切特性及其影响因素分析

针对某大型水电站揭露的原状层间错动带试样,模拟现场快速施工可能会产生的不排水边界条件,在围压5～30 MPa的高压力条件下开展了不固结不排水三轴试验,并结合试样物理性质的差异,分析讨论了原状层间错动带的力学特性。试样试验曲线和破坏模式主要由高围压控制：其应力-应变关系曲线均为应变硬化型且破坏后呈腰鼓状为塑性破坏。此外,较湿颗粒发生了大规模的颗粒破碎,其是造成高饱和度试样强度包线的趋势线随围压降低的根本原因。试验结果明显受物理性质影响造成了试验数据离散性,敏感性分析表明,围压P和饱和度 对初始弹性模量 和破坏强度 的影响最大,其次是孔隙比e,颗粒粒径（ ）分布对其影响程度最小。根据试样剪切特性建立的强度特征（ 和 ）初步预测公式可供实际工程参考。