新疆某地浸砂岩型铀矿中铀赋存形态的研究

以新疆某地浸砂岩型铀矿为研究对象,参考Tessier逐级化学提取方法,对10件矿芯试样进行铀赋存形态的研究。将铀赋存形态分为可交换离子态、碳酸盐结合态、铁锰氧化物结合态、硫化物及有机物结合态和残渣态,其中前4种形态铀为活性铀,残渣态铀为惰性铀。研究结果显示,无论是试样间还是同一试样内,铀的形态分布特征都存在明显的差异。各形态铀的含量(平均值)占总量铀的比例为:残渣态(37.75%,RSD为1.80%)>碳酸盐结合态(20.56%,RSD为2.72%)>可交换离子态(15.51%,RSD为1.85%)>硫化物及有机物结合态(14.26%,RSD为2.08%)>铁锰氧化物结合态(11.91%,RSD为1.75%),表明残渣态铀是砂岩型铀矿石中铀的重要赋存形式。针对目前酸法地浸工艺,活性铀是可被浸出的部分,而惰性铀对资源回收是无效的,对于残渣态铀所占比例较高的铀矿石,铀的浸出值较低,在地浸过程中依靠提高溶浸剂的酸度和增加氧化剂对提高浸出率是无益的。     

河套平原沉积物中铀的赋存形态及其与地下水铀浓度的关系

采用Tessier的五步提取法,对位于河套平原杭锦后旗沙海乡四个钻孔沉积物进行铀的五个赋存形态(包括可交换态、碳酸盐吸附态、铁锰氧化物吸附态、有机物或硫化物吸附态和基质态)分布特征研究。结果发现,铁锰氧化物结合态铀含量为0.140~0.328 mg/kg,占总铀量的34.7%;基质态中铀的含量为0.256~0.405 mg/kg,占44.0%。对于铁锰氧化物结合态,铀含量与铁、锰含量呈正相关性,其中铀与铁线性相关系数0.311~0.482,铀与锰线性相关系数0.506~0.642。表明,沉积物中锰氧化物对铀含量的影响大于铁氧化物对铀含量的影响。进一步研究发现,沉积物岩性对铀含量的影响较大,总铀在细砂中平均含量为0.088 mg/kg,在黏土中平均量为0.260 mg/kg。不同深度地下水中铀浓度和沉积物铀含量的研究表明,随深度增加,地下水中铀浓度与含水层沉积物中铀含量均呈降低的趋势。地下水中铀浓度受含水层中可交换态铀含量的直接影响。     

呼和浩特市大气降尘中镉赋存形态分析

采用Tessier连续提取法对呼和浩特市不同区域的9个大气降尘样品中镉的赋存形态进行了研究。结果表明,各形态含量在总镉中所占比例由大到小排列顺序依次是:铁锰氧化物结合态>残渣态>碳酸盐结合态>强有机结合态>可交换态。大气降尘中镉的5种形态占总镉的平均质量分数由大到小为:铁锰氧化物结合态31.80%,残渣态24.42%,碳酸盐结合态19.04%,强有机结合态14.61%,可交换态10.13%;铁锰氧化物结合态是主要存在形态;铁锰氧化物结合态镉、有机结合态镉、残留态镉这三种形态镉生物有效性很低,但当环境改变时可能发生镉释放,应予以关注。汽油和煤的燃烧以及工厂排放镉能加大城市大气降尘中的镉含量。     

北京市街道灰尘中重金属元素赋存状态及环境效应

采用Tessier的五步提取法,对北京北西—南东剖面所采集的街道灰尘样品粒度≤100μm组分中As、Cd、Cr、Hg、Pb和Zn等6元素的5个形态(可交换态、碳酸盐结合态、铁锰氧化物结合态、有机物结合态、残渣态)的分布特征研究发现,在可交换态和碳酸盐结合态中Cd的含量比都为最高,Pb、Hg、Zn和As在有机物结合态中含量比相近,铁锰氧化物结合态中Pb所占比例最高,而As和Cr主要存在于残渣态中。6种街道灰尘污染元素的相对活动性和潜在生物利用度顺序为:Cd>Zn>Pb>Cr>Hg>As。     

深港西部通道填海区淤泥重金属化学形态分析

以深港西部通道填海区淤泥为研究对象,研究了重金属的化学形态特征,分析了填海工程活动带来的填海区地下水物理化学条件变化对重金属各个形态的影响。结果表明:除残留态外,填海区重金属存在形态主要为铁锰结合态、碳酸盐结合态和硫化物及有机结合态,其中,Pb和Ni以铁锰氧化物结合态和碳酸盐结合态为主,Cu以碳酸盐结合态和有机结合态为主,Zn以有机结合态和铁锰氧化物结合态为主,而Cd则以碳酸盐结合态为主。各金属在深港西部通道填海区淤泥的潜在迁移能力序列如下:Pb(39.68%)>Cu(31.59%)>Zn(20.49%)>Cd(12.80%)>Ni(10.98%)。     

生态地球化学土壤样品元素形态分析方法研究

对生态地球化学土壤样品,采用振荡提取法提取样品中离子交换态(包括水溶态)、碳酸盐结合态、腐殖酸结合态、铁锰氧化物结合态、强有机质结合态(包括部分硫化物);采用等离子体发射光谱法测定其中Cd、Co、Cr、Cu、Mn、Mo、Ni、Pb、Zn,原子荧光光谱法测定As、Hg、Sb、Se。方法的质量参数满足生态地球化学土壤样品评价形态分析的需要。     

富硒土壤镉的赋存状态

采用7步提取法对某地富硒土壤样品进行镉的形态分析,发现镉质量分数较高,镉平均为0.374 mg/kg,最高为0.943 mg/kg。各形态含量差异较大,基本是残渣态离子交换态铁锰氧化物结合态腐殖酸结合态强有机结合态碳酸盐态水溶态,在7种形态中以残渣态、离子交换态、铁锰氧化物结合态3种形态占主导。     

四川某地碳硅泥岩型铀矿中铀的赋存形态研究

以四川某地碳硅泥岩型铀矿为研究对象,通过对8件岩芯样品进行铀赋存形态的研究。将铀赋存形态分为可交换态、铁锰结合态、碳酸盐结合态、有机态和残渣态,其中前四种铀为活性铀,残渣态为惰性铀。研究结果显示,无论是在试样内、试样间,还是同一矿床的不同层位以及不同的矿床间铀赋存形态的含量都有明显的差异。     

四川某地碳硅泥岩型铀矿中铀的赋存形态研究

以四川某地碳硅泥岩型铀矿为研究对象,通过对8件岩芯样品进行铀赋存形态的研究。将铀赋存形态分为可交换态、铁锰结合态、碳酸盐结合态、有机态和残渣态,其中前四种铀为活性铀,残渣态为惰性铀。研究结果显示,无论是在试样内、试样间,还是同一矿床的不同层位以及不同的矿床间铀赋存形态的含量都有明显的差异。     

离石黄土对Cr3+的去除及对Cr3+形态分布的影响

选取离石黄土中的黄土及黏土层和重金属铬作为研究对象,通过等温吸附实验及Tessier法形态提取实验,分析了Cr3 在离石黄土中的存在形态,并对其分布规律进行了比较,研究了离石黄土对Cr3 的去除机理.实验结果表明:黄土及黏土层对Cr5 均有很好的去除效果,吸附率超过98%.当初始质量浓度ρ0＜100 mg/L时,其等温吸附曲线属Henry型.形态提取研究发现:黄土及黏土层对Cr3 的吸附形态以碳酸盐结合态和铁锰氧化物结合态为主,两者的总和都在95%以上,有机质结合态较少且相对稳定.受黄土及黏土层化学成分差异的影响,它们对Cr3 的去除在形态分布上存在一定差异,黄土中Cr3 的形态分布:碳酸盐结合态＞铁锰氧化物结合态＞有机质结合态＞可溶态＞可交换态;黏土层中Cr3 的形态分布:铁锰氧化物结合态＞碳酸盐结合态＞有机质结合态＞可溶态＞可交换态.     

Trace Metal Speciation of USGS Reference Sample MAG-I

The USGS reference sample marine mud MAG-1 has been subjected to a sequential extraction procedure designed to partition the constituent trace metals into five fractions: I-exchangeable; II- bound to carbonates; III-bound to Fe-Mn oxides; IV- bound to organic matter; V- residual. The analytical approach involved successive chemical extractions and the subsequent determination of trace metal concentrations (Co, Cu, Ni, Pb, Zn; Fe, Mn) in the leachates by atomic absorption spectrophotometry. The chemical speciation results obtained on four replicate sub-samples demonstrate that the coefficients of variation for metal concentrations in the individual fractions are generally better than + 10%. Comparison with published values for total trace metal concentrations in the MAG-1 sample suggests that the overall accuracy of the chemical extraction procedure is satisfactory.     

太湖沉积物中重金属的地球化学形态及特征分析

用连续提取法分析了太湖沉积物5种重金属的地球化学形态,对地球化学形态的组成和地理特征进行了分析研究.重金属地球化学形态配分的共同特点是可交换态最低,残渣态最高.两种形态中Cd的可交换态最高,Cr的残渣态最高,可交换态最低.Cd的碳酸盐态较高,Cr的最低;Pb、Cd的Fe-Mn氧化态较高,Cu的偏低;Cu的有机态最高,Cd的最低;Zn的地球化学形态比例大都处于中间.地域上变化较大的元素是Cd和Cu,变化不明显的元素有Pb和Zn.化学成分中Fe2O3、MnO与重金属地球化学形态的相关性最好,TOC与Cu的形态相关系数最高.综合对比分析表明,太湖沉积物重金属的生物有效性以Cd为最高,其次为Pb.     

Geochemistry of rare earth elements in the mainstream of the Yangtze River,China

Water, suspended matter, and sediment samples were taken from 8 locations along the Yangtze River in 1992. The concentration and speciation (exchangeable, bound to carbonates, bound to Fe–Mn oxides, bound to organic matter, and residual forms) of rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb, and Lu) were determined by instrumental neutron activation analysis (INAA).The contents of the soluble fraction of REEs in the river are low, and REEs mainly reside in particulate form. In the particles, the chondrite-normalized distribution patterns show significant LREE enrichment and Eu-depletion. While normalized to shales, both sediments and suspended matter samples show relative LREE enrichment and HREE depletion. REEs are relatively enriched in fine-grained fractions of the sediments.The speciation characteristics of REEs in the sediments and suspended matter are very similar. The amount of the five forms follows the order: residual>>bound to organic matter∼bound to Fe–Mn oxides>bound to carbonates>>exchangeable. About 65 to 85% of REEs in the particles exist in the residual form, and the exchangeable form is very low. High proportions of residual REEs reveal that REEs in sediments and suspended matter are controlled by their abundances in the earth's crust. Carbonate, Fe–Mn oxide and organic fractions of REEs in sediments account for 2.4–6.9%, 5.2–11.1%, and 7.3–14.0% of the total contents respectively. They are similar to those in the suspended matter. This shows that carbonates, Fe–Mn oxides and organic matter play important roles during the particle-water interaction processes. By normalization to shales, the 3 forms of REEs follow convex shapes according to atomic number with middle REE (Sm, Eu, and Tb) enrichment, while light REE and heavy REE are depleted.     

龙感湖稀土元素的地球化学特征

采用液-液萃取法,连续提取法和ICP-MS测试技术,对龙感湖不同季节水和颗粒物中稀土元素进行研究.结果表明,龙感湖的溶解态稀土含量极低,稀土总含量(ΣREE)在3.14～129.81ng/kg之间,且季节性变化明显.龙感湖溶解态稀土元素表现出平坦型的页岩配分模式,这是由于在草型湖泊中溶解态稀土主要以吸附在微细胶体上的形式存在,水粒相互作用在这个过程中起主要控制作用.悬浮物中的稀土含量顺序为:残渣态>>Fe-Mn结合态>>有机态和AEC态,颗粒物中稀土元素主要以残渣态形式存在.Fe-Mn结合态、有机态和AEC态的页岩配分模式为中稀土富集,残渣态的页岩配分模式为平坦型.这说明中稀土与轻重稀土相比具有更强的潜在地球化学活性,但在龙感湖的环境中的迁移能力相对轻重稀土来说较弱.     

Particulate trace metal speciation in stream sediments and relationships with grain size: Implications for geochemical exploration

Sediment samples were collected from streambeds in an undisturbed watershed in eastern Quebec (Gaspé Peninsula). Two sampling sites were located on a stream draining an area of known mineralization (Cu, Pb, Zn) and two on a control stream. The sediment samples were separated into 8 distinct size classes in the 850 μm to <1 μm size range by wet sieving, gravity sedimentation or centrifugation. Each sediment subsample was then subjected to a sequential extraction procedure designed to partition the particulate heavy metals into five fractions: (1) exchangeable; (2) specifically adsorbed or bound to carbonates; (3) bound to Fe-Mn oxides; (4) bound to organic matter; (5) residual. The following metals were analyzed in each extract: Cu, Pb, Zn; Fe, Mn.Comparison of samples from the mineralized area with control samples revealed the expected increase in total concentrations for Cu, Pb and Zn. Non-detrital metals were mainly associated with Fe oxides (specifically adsorbed; occluded) and with organic matter or resistant sulfides. For a given sample, variation of trace metal levels in fractions 2 and 3 with grain size reflected changes in the available quantities of the inorganic scavenging phase (FeOx/MnOx); normalization with respect to Fe and Mn content in fraction 3 greatly reduced the apparent dependency on grain size.The results of this study suggest that a single reducing extraction (NH₂OH.HCl) could be used advantageously to detect anomalies in routine geochemical surveys. A second leaching step with acidified H₂O₂ could also be included, as the trace metal concentrations in fraction 4, normalized with respect to organic carbon content, also showed high {anomaly/background} ratios.     

煤及其转化产物中重金属形态分布研究

参考Tessier形态分析程序,对煤及其转化产物中的Mn、Mo和Pb的存在形态进行了实验研究,为原煤使用形态转化中的环境效应评价提供参考。结果表明,Mn、Mo和Pb在原煤、煤焦、气化灰、燃煤灰中的形态变化依次为：可交换态、碳酸盐结合态比例下降,铁锰水合氧化物结合态比例上升;各元素的可交换态和碳酸盐结合态含量之和在原煤、气化灰、燃煤灰中依次减少;对原煤和煤焦中的有机态重金属的重复及高提取剂浓度提取是有效的。     

Chemical partitioning of trace and major elements in soils contaminated by mining and smelting activities

Soils from historical Pb mining and smelting areas in Derbyshire, England have been analysed by a 5-step sequential extraction procedure, with multielement determination on extraction solutions at each step by ICP-AES. Each of the chemical fractions is operationally defined as: (i) exchangeable; (ii) bound to carbonates or specifically adsorbed; (iii) bound to Fe–Mn oxides; (iv) bound to organic matter and sulphides; (v) residual. The precision was estimated to be about 5%, and the overall recovery rates were between 85 and 110%. The carbonate/specifically adsorbed and Fe–Mn oxide phases are the largest fractions for Pb in soils contaminated by both mining and smelting. Most of the Zn is associated with Fe–Mn oxide and the residual fractions. Cadmium is concentrated in the first 3 extraction steps, particularly in the exchangeable phase. The most marked difference found between soils from the mining and smelting sites is the much higher concentrations and proportions of metals in the exchangeable fraction at the latter sites. This indicates greater mobility and potential bioavailability of Pb, Zn and Cd in soils at the smelting sites than in those in the mining area. The most important fraction for Fe and Al is the residual phase, followed by the Fe–Mn oxide forms. In contrast, the Fe–Mn oxide fraction is the dominant phase for Mn in these soils. In the mining area, most of the Ca is in the carbonate fraction (CaCO₃), while the exchangeable and residual phases are the main fractions for Ca at the smelting sites. Phosphorus is mainly in the residual and organic fractions in both areas. The exchangeable fractions of Pb, Zn and Cd in soils were found to be significantly related to the concentrations of these metals in pasture herbage.