Characteristics of Coal Ashes in Yanzhou Mining District and Distribution of Trace Elements in Them

In the process of combustion of coal organic and inorganic materials in it will undergo a complex variation.Part of thew will become volatiles and,together with coal smoke,enter into atmosphere,some will remain in micro-particulates such as ash and dust and find their way into atmosphere in the form of solid particles,and the rest will be retained in ash and slag.Coal ashes are the residues of organic and inorganic substances in coal left after coal combustion and the compostition of coal ashes in dependent on that of minerals and organic matter in coal.This paper deals with the chemical composition of coal ashes,the distribution of trace elements in them and their petrological characteristics,and also studies the relationship between the yield of coal ashes and the distribution of trace elements.In addition,a preliminary study in also undertaken on the factors that affect the chemical composition of coal ashes.As viewed from the analyses of coal ash samples collected from the Yanzhou mining district,it can be seen clearly that coal ashes from the region studied are composed chiefly of crystalline materials,glassy materials and uncombusted organic matter and the major chemical compositions are SiO2,Al2O3,Fe2O3,and CaO,as well as minor amounts of SO3,PWO5,Na2O,K2O and TiO2.During the combustion of coal,its trace elements will be redistributed and most of them are enriched in coal ashes.At the same time,the concentrations of the trace elements in flying ash are much higher than those of bottom ash,i.e.,with decreasing particle-size of coal ashes their concentrations will become higher and higher.So the contents of trace elements are negatively proportional to the particle-size of coal ashes.There has been found a positive correlation between the trace elements Th.V.Zn,Cu and Pb and the yield of coal ashes while a negative correlation between Cl and the yield of coal ashes.     

四种前处理方法对电感耦合等离子体质谱测定植物样品中27种微量元素的影响

采用HNO₃-HClO₄-HF常压消解、HNO₃-H₂O₂-HF高压密闭消解、HNO₃-H₂O₂微波消解,干法灰化后残渣用HNO₃-HF-HClO₄溶解等四种方法对植物样品进行前处理,使用电感耦合等离子体质谱(ICP-MS)对植物样品中的27种元素进行定量分析,探讨了不同前处理方法对ICP-MS测定植物样品中微量元素的影响。分析结果表明: HNO₃-HClO₄-HF常压消解使用大量试剂,污染环境,造成空白值高;在常压体系中HClO₄的加入能提高样品的消解效率,但赶酸不完全,会造成复合离子对钒和砷的干扰;干法灰化过程中某些元素(硼、汞等)会损失;常压消解和高压密闭消解中加入HF能有效地提高铍、稀土、钇、钛、锑、铀等元素的回收率,但在蒸干赶HF的过程中,会造成硼和汞的损失,并且钢套的生锈会造成铬、镍空白值高。尽管没有一种方法能适用于所有元素的分析,但相比较而言,HNO₃-H₂O₂微波消解体系操作简单,大部分元素(除铍、钛、锑、铋、稀土)能得到满意的结果,精密度(RSD)均小于10%(n=10),相对误差(RE)为-4.6%~13.6%。     

Mineralogical and geochemical characteristics of coal ash from the Northwest Thrace region,Turkey: a case study

The first combined mineralogical and geochemical investigation of coal ashes from the Northwest Thrace Coal Basin, Turkey, was performed as a case study. The coal ash samples were obtained at 525 °C (group I), 750 °C (group II), and 1000 °C (group III) ashing temperatures from coal samples from the basin and were studied in terms of their mineralogical and geochemical composition using XRD and ICP-MS methods. The determination of the mineralogical composition was done for all of the groups; the geochemical analysis was carried out only for group II. In accordance with the high SiO₂, Fe₂O₃, CaO, and SO₃ content of the ash, quartz (SiO₂), hematite (Fe₂O₃), and anhydrite (CaSO₄) are the major crystalline phases for all of the ash groups. The other minerals are muscovite, thenardite, tridymite, calcite, wollastonite, anorthite, cristobalite, gibbsite, ternesite, mullite, nahcolite, and nacrite. High-temperature phases such as mullite, wollastonite, and anorthite were observed at 750 and 1000 °C. According to the (Fe₂O₃ + CaO + MgO+ K₂O+ Na₂O)/(SiO₂ + Al₂O₃+ TiO₂) ratios varying from 0.19 to 5.65, the ashes are highly prone to slagging. Compared to average values of low-rank coal ashes, the contents of V, Cr, Co, Ni, Zn, As, Rb, Sr, Mo, Cs, W, and U of the ash are higher, whereas the total content of rare earth elements (REEs) (Σ 163.7 ppm) are lower. Based on upper continental crust normalization, As, Se, Th, and U are enriched in all of the samples. The higher trace element contents in the ashes might be considered as a possible health hazard. The correlation analyses indicated that Ca is associated with anhydrite and As with hematite. The correlation analyses also showed that newly formed Al and Ca silicates may contain the elements such as Ti, K, Na, Cr, Sn, and Pb.     

氢化物发生-电感耦合等离子体发射光谱法测定铀矿地质样品中痕量硒

采用氢化物发生技术测定地质样品中的硒时,需要考虑样品的溶解、Se价态的预还原以及抑制共存离子的干扰。本文采用硝酸-盐酸-氢氟酸-高氯酸体系快速溶解样品,直接加入浓盐酸煮沸将六价硒还原为四价硒,将氢化物发生器与电感耦合等离子体发射光谱仪联用测定了铀矿地质样品中的痕量硒。样品中除了Cu2+其他离子的含量均不干扰硒的测定,通过在试液中加入铁盐溶液或在硼氢化钠还原剂中加入铁氰化钾抑制了Cu2+的干扰。方法检出限为0.12μg/L,精密度(RSD)小于5%。与前人报道的方法相比,本方法检出限较低,操作简单快速,冲洗30 s可消除记忆效应,适合批量铀矿地质样品中痕量硒的测定。     

X射线荧光光谱法分析不同类型岩石中10种主量元素的测试能力验证

以28个不同类型岩石标样作外标,用玻璃熔片法制样,采用经验系数法进行基体校正,建立了X射线荧光光谱法(XRF)测定不同类型岩石中硅铝钙镁等10种主量元素的分析方法。该方法被用于参与GeoPT分析测试能力验证,15年来分析了23个不同类型的岩石验证样品。经验证该方法对SiO_2、Al_2O_3、K_2O和CaO具有非常好的分析效果(所有测定结果的|Z|2);对于MgO、MnO、TiO_2和Na_2O四个元素,尽管各有一个样品的分析结果的|Z|2,这主要是样品与标样的基体差异较大造成了低含量样品测定结果超差,但依然可获得好的分析效果;当TFe_2O_31.0%,P_2O_5含量在0.08%~0.80%区间时,分析结果的|Z|2,满足分析期望。总体上所建立的XRF分析方法稳定,可满足应用地球化学实验室测试不同类型岩石中10种主量元素的分析期望。     

Preparation of Four Chromium Ore Reference Materials

The preparation and characterisation of four chromium ore reference materials are described in this paper. The sample material for GCr‐1, GCr‐3 and GCr‐4 was collected from chromite deposits in Tibet, Qinghai province and Inner Mongolia. GCr‐2 is a composite sample from GCr‐1 and GCr‐4. Sample homogeneity was tested by WD‐XRF and the relative standard deviations were < 1.0%. An F‐test showed that all four materials were homogeneous. Thirteen laboratories involved in the inter‐laboratory programme provided 672 determinations (eighteen oxides and elements). Sixteen components were characterised as certified values, of which Cr₂O₃ ranged from 17.59 to 57.80% m/m. The contents of FeO and CO₂ were taken as reference values.     

CaAl2Si2O8 polymorphs: Sensitive geothermometers and geospeedometers

Plagioclase is the major rock-forming mineral constituting the Earth’s crust, whereas anorthite (CaAl₂Si₂O₈) is a common minerals in lunar highlands crust, meteorites, possibly in some comets and on Mercury. Besides anorthite, two high-temperature polymorphs of CaAl₂Si₂O₈ are known: dmisteinbergite and svyatoslavite, which are found in burnt coal dumps, meteorites and pseudotachylytes. Here we present the results of detailed studies (quenching experiments, elemental analysis, Raman spectroscopy and in situ high temperature single crystal X-ray diffraction (up to 1000 °C)) on naturally co-occurring CaAl₂Si₂O₈ polymorphs (anorthite, dmisteinbergite and svyatoslavite) from a burnt coal dump in Kopeisk, Russia. New polymorphs were found in all natural samples and obtained upon heating of dmisteinbergite (unquenchable β-dmisteinbergite and quenchable γ-dmisteinbergite). It was shown that Ca coordination differs significantly in CaAl₂Si₂O₈ polymorphs, resulting in a different capacity to host Ba and possibly other large ion lithophile elements. Combining our data on natural samples with the previously published data on natural and synthetic compounds, we propose a new scheme of CaAl₂Si₂O₈ polymorphs stability. Our results indicate that CaAl₂Si₂O₈ polymorphs could be used for temperature estimations for both Earth and planetary sciences.     

Simultaneous Determination of Major and Trace Elements in Fused Volcanic Rock Powders Using a Hermetic Vessel Heater and LA‐ICP‐MS

Fused glass prepared without the addition of a flux is generally more homogeneous than a pressed powder pellet and thus ideal for analysis of bulk samples by LA‐ICP‐MS. In this work, a new glass‐making method using a boron nitride crucible was developed to prepare homogenous glass samples from silicate rock powder. The apparatus consisted of a small boron nitride vessel with net volume of about 34 mm³ and two molybdenum strips. Applying the summed metal oxide normalisation technique, both major and trace element contents in the fused glass were measured by LA‐ICP‐MS. Analyses of five geochemical reference materials (spanning the compositional range basalt–andesite–rhyolite) indicated that the measured SiO₂, Al₂O₃ and P₂O₅ contents matched the preferred values to within 5%, and the other major elements generally matched the preferred values to within 8%. Except for the transition metals, the measured trace element contents generally matched the preferred values to within 10%. Compared with the iridium heater method developed by Stoll et al. (2008), element volatilisation during high‐temperature melting was effectively suppressed in our method, but metal segregation caused by reduction of BN may cause loss of Cr, Ni and Cu. Although analysis with a large spot size has the advantage of improving counting statistics, matrix effects induced by mass loading of the ICP may hamper the accurate determination of some elements.     

CO and CO2 emissions from spontaneous heating of coal under different ventilation rates

Carbon monoxide (CO) and carbon dioxide (CO₂) emissions during a spontaneous heating event in a coal mine are important gases to monitor for detecting the spontaneous heating at an early stage. However, in underground coal mines, the CO and CO₂ concentrations and their related fire ratios may be affected by mine ventilation. In this study, CO and CO₂ emissions from spontaneous heating of a U.S. coal sample were evaluated in an isothermal oven under different airflow ventilation rates ranging from 100 to 500 cm³/min. Laboratory experiments were conducted at oven temperatures of 70, 90, and 100 °C. The temperature at the center of the coal sample was continually monitored, while the CO, CO₂, and oxygen (O₂) concentrations of the exit gas were continually measured. The results indicate that CO was generated immediately after the airflow passed through the coal, while CO₂ was generated in a late phase. The amounts of CO generated under different airflow rates were approximately the same at the initial temperature of 70 °C, while the amounts of CO generated increased significantly as the airflow rates and initial temperatures increased. The ratio of CO/CO₂ was found to be independent of airflow rate and initial temperature, approaching a constant value of 0.2 quickly if there was no thermal runaway. The value tended to decrease when a thermal runaway took place. The CO/O₂ deficiency ratio was dependent on both airflow rates and the initial temperature. The experimental results are in qualitative agreement with some large-scale test and field monitoring results.     

Chemical and petrographical characterization of feed coal, fly ash and bottom ash from the Figueira Power Plant, Paraná, Brazil

The aim of the present study is the petrographic and chemical characterization of the coal at the Figueira Power Plant, Paraná, Brazil, prior and after the beneficiation process and the chemical characterization of fly and bottom ashes generated in the combustion process.Petrographic characterization was carried out through maceral analysis and vitrinite reflectance measurements. Chemical characterization included proximate analysis, determination of calorific value and sulphur content, ultimate analysis, X-ray diffraction, X-ray fluorescence, Inductively Coupled Plasma — Mass Spectrometry (ICP-MS) and Inductively Coupled Plasma — Atomic Emission Spectrometry (ICP-AES) analysis, and determination of Total Organic Carbon (TOC) content.Vitrinite reflectance analyses indicate a high volatile B/C bituminous coal (0.61 to 0.73% Rrandom). Maceral analyses show predominance of the vitrinite maceral group (51.6 to 70.9 vol.%, m.m.f). Except of the Run of mine (ROM) coal sample, the average calorific value of the coals is 5205 kcal/kg and ash yields range from 21.4 to 38.1 wt.%. The mineralogical composition (X-ray diffraction) of coals includes kaolinite, quartz, plagioclase and pyrite, whereas fly and bottom ashes are composed by mullite, ettringite, quartz, magnetite, and hematite. Analyses of major elements from coal, fly and bottom ashes indicate a high SiO₂, Al₂O₃, and Fe₂O₃ content. Trace elements analysis of in-situ and ROM coals by ICP-MS and ICP-AES show highest concentration in Zn and As. Most of the toxic elements such as As, Cd, Cr, Mo, Ni, Pb, and Zn are significantly reduced by coal beneficiation. Considering the spatial distribution of trace elements in the beneficiated coal samples, which were collected over a period of three months, there appears to be little variation in Cd and Zn concentrations, whereas trace elements such as As, Mo, and Pb show a larger variation.In the fly and bottom ashes, the highest concentrations of trace elements were determined for Zn and As. When compared with trace element concentrations in the feed coal, fly ashes show a significant enrichment in most trace elements (As, B, Be, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Sb, Tl, and Zn), suggesting a predominantly volatile nature for these elements. In contrast, Sn is distributed evenly within the different ash types, whereas U shows depleted concentration in both bottom and fly ash samples.According to the International Classification of in-seam coals the Cambuí coals are of para/ortho bituminous rank of low grade (except for the ROM sample), and are characterized by the predominance of vitrinite macerals.     

微波消解-电感耦合等离子体质谱法测定煤中的硼

煤中硼的准确测定对于研究成煤的沉积环境具有重要意义。微波消解-电感耦合等离子体质谱(ICP-MS)可以有效地测定煤中的大部分微量元素,但由于硼易挥发等特殊的物理化学性质,致使硼的测定过程较为繁琐,测试结果不够准确。本文对微波消解ICP-MS测定煤中硼含量的分析方法进行了改进。样品中加入磷酸、硝酸和氢氟酸,用微波消解仪消解完全,置于电热板加热赶酸完毕后用硝酸提取。硼的卤化物易挥发,磷酸的加入使硼与磷酸结合生成难挥发的稳定络合物,起到了固硼的作用。ICP-MS测定中采用铍作为内标,通过在线加入的方式有效地补偿了基体效应产生的影响;用稀氨水冲洗进样系统,很好地降低了硼的记忆效应;选择高分辨率模式来测定,避免了12C和40Ar4+等质谱峰的干扰。方法的仪器检出限(0.22ng/mL)和方法检出限(0.34 ng/mL)较低,方法精密度(RSD)小于0.6%,灵敏度高,且测定标准样品的准确度良好。该方法简单快速,适用于批量分析煤样中硼的含量。     

Preparation and Certification of Biogeochemical Reference Materials

The Institute of Geophysical and Geochemical Exploration in China recently prepared ten biogeochemical certified reference samples GSB1‐10 (CRMs). The samples are primary agricultural products such as rice, wheat, corn, soybean, cabbage, spinach, tea, powder, chicken and apple. Lyophilisation technology and a high‐alumina ball mill were used to process the samples. Fourteen laboratories and hundreds analysts in China participated in the certification analysis. Over ten reliable analytical methods, predominately ICP‐MS, ICP‐AES and INAA, were used for analysing the samples for fifty‐nine elements. A total of 22477 determinations led to 5136 average data sets. Certified values of fifty‐four elements were assigned.     

Mineralogical composition and ash geochemistry of raw and beneficiated high sulfur coals

Coal is one of the most available energy sources on earth. The mineralogical and geo-chemical aspects of coals are of prime importance for their utilization. The mineralogical composition, ash chemistry, and ash fusion temperature (AFT) ranges of raw and beneficiated coals are investigated in this paper. Further, the mineral matter transformation during the beneficiation processes viz. by oxidative desulfurization; alkali extraction and ultrasonication along with the relationship of the ash fusion temperature (AFT) ranges with the ash components in the coal are discussed. The major oxides present in the coal and beneficiated coal ashes include Fe₂O₃, Al₂O₃, SiO₂, CaO, and MgO, which significantly affect the ash fusion temperature ranges. Initial deformation temperature (IDT) changes with the ash components and, increases with the increase in the Fe₂O₃ content in coal ash. With increasing concentrations of both Al₂O₃ and SiO₂, the initial deformation temperature (IDT) also increases. The increasing and decreasing nature of the initial deformation temperature (IDT) observed is also dependent upon the CaO and MgO contents. XRD analysis of the coal samples revealed significant changes in mineral matter contents with the types of beneficiation processes adopted for coal. The minerals like chlorite, illite, montmorillonite, pyrite, calcite, aragonite, and alumina have been removed during the beneficiation processes. The FTIR spectra also indicate the presence of minerals like gypsum (G), calcite (C) aragonite (Ar), quartz (Q) and kaolinite (K) in the raw coal and their subsequent removal after the beneficiation processes.     

REE Tetrad Effect as a Powerful Indicator of Formation Conditions of Karst Bauxites: A Case Study of the Shahindezh Deposit,NW Iran

Study of the concentration of major, trace, and rare earth elements (REE) in the Shahindezh karst bauxite deposit, northwestern Iran clarifies the relationship of the tetrad effect with geochemical parameters in the bauxite ores. The existence of irregular curves in the chondrite-normalized REE patterns as well as non-CHARAC behavior of geochemically isovalent pairs (Y/Ho) are related to the tetrad effect. The meaningful positive correlation between the sizes of the calculated T3 tetrad effect and some geochemical factors such as Y/Ho, ΣREE, La/Y, (La/Yb)N, and (LREE/HREE)N as well as some major oxides-based parameters like Al2O3 + LOI/SiO2 + Fe2O3, Al2O3/Fe2O3, Al2O3 + LOI, IOL, and SiO2 + Fe2O3 indicate that the studied bauxite horizon was likely deposited by different (acidic and/or alkalic) solutions at different stages. The lower part of the studied horizon with a thickness of ~4.7 m displays alkali characteristics whereas the upper parts of the horizon with a thickness of ~5.3 m are characterized by more acidic conditions. These results are fully supported by the co-occurrence of convex-concave tetrad effect curves in the chondrite-normalized REE patterns. Therefore, the tetrad effect phenomenon used in this study has proved to be a good and reliable geochemical proxy to assess the conditions of the depositional environment in the Shahindezh bauxite ores.     

Assessment of Dissolution of Silicate Rock Reference Materials with Ammonium Bifluoride and Nitric Acid in a Microwave Oven

The complete dissolution of representative test portions of powdered rock samples for the determination of the mass fractions of trace elements by ICP‐MS relies either on aggressive and time‐consuming acid digestions or fusion/sintering with appropriate fluxes. Here, we evaluate a microwave oven dissolution method that employs a solution of NH₄HF₂ and HNO₃. The entire procedure occurs in a closed vessel system and takes up to 4 h. In hundreds of digestions, the precipitation of fluorides was never observed. Replicate decomposition of 100 mg of twenty‐one international reference materials (RMs) of igneous rocks, and also one of a shale presented mostly satisfactory recoveries of forty‐one trace elements. Important exceptions were Zr and Hf in G‐2 and GSP‐2 (mean recoveries of ca. 70%), although for four other felsic rock RMs, the digestion was complete. For ultramafic rock RMs, we present Cr results that indicate quantitative dissolution of Cr‐bearing phases. We discuss the findings and conclude that advances in sample preparation of geological materials for instrumental analysis would benefit from a better understanding of how specific characteristics, such as composition and crystallinity of certain minerals, may affect their reactivity.     

Geochemical Characteristics of Eolian Deposits in the Chengdu Plain of Sichuan Province and the Implications for Provenance

In this study Chengdu Red Earth （CRE） from the Chengdu Plain （CP）,Sichuan province,was analyzed for its elemental （major and trace elements） and isotopic （Sm-Nd） geochemistry and compared with Pleistocene loess and paleosol samples from the Chinese Loess Plateau （CLP） in Northern China.The geochemical composition of CRE is similar to north China loess,and also resembles the average UCC.This indicates that CRE,as loess deposits in Northern China,was derived from well-mixed sedimentary protoliths that have undergone numerous upper crustal recycling processes.However,obvious differences in the geochemical characteristics of CRE and the north China loess are also revealed in our results.For chemically stable elements,CRE has higher Ti,Zr,Hf and lower ΣREE,Ba contents in comparison with loess samples from the CLP.Further analysis shows that CRE has higher TiO2/Al2O3,SiO2/Al2O3,Ba/Rb and lower Ce/Yb,Eu/Yb,LaN/YbN and ΣLREE/ ΣHREE ratios.In Sm-Nd isotopic geochemistry,Sm and Nd content and the εNd（0） value in CRE are significantly higher than those in north China loess.The higher TiO2 content in CRE coincided with a high background concentration of Ti in the Sichuan Basin and the surrounding regions.The lower ΣREE and higher Sm,Nd,εNd（0） values are related to the wide distribution of basalt in the southwest Sichuan Basin.The elemental and isotopic geochemistry of CRE indicates that eolian materials in the CP predominantly come from the Sichuan Basin and the surrounding regions,which differs from loess deposits in the CLP.     

The major‐ and trace‐element whole‐rock fingerprints of Egyptian basalts and the provenance of Egyptian artefacts

Discrimination diagrams have been developed that source Egyptian basaltic artefacts using whole‐rock major element geochemistry. These include K₂O versus SiO₂, TiO₂ and P₂O₅ against MgO/Fe₂O₃^t (total Fe as Fe₂O₃), and a discriminant analysis diagram using SiO₂, Fe₂O₃^t, CaO, and MnO. A complementary set of diagrams uses easily obtained trace element data (Nb/Y versus Zr/Nb; Zr [ppm] versus Rb/Sr; TiO₂ [wt % volatile free] versus V; and Cr [ppm] versus Zr/Y) to determine the bedrock sources. These diagrams have been applied to seven First Dynasty basalt vessels (Abydos), two Fourth Dynasty basalt paving stones (Khufu's funerary temple, Giza), and two Fifth Dynasty paving stones (Sahure's complex, Abu Sir). They show that the bedrock source for all the artefacts was the Haddadin flow in northern Egypt. Multidimensional scaling and cluster analysis applied to the whole‐rock data (major elements and trace elements together) and previously published mineral fingerprinting studies confirm these results. Comparing mineral versus whole‐rock fingerprinting techniques, a major advantage of the former is the small sample size required (0.001 g compared to ≥ 0.1 g). Analytical costs are similar for both methods assuming that a comparison (bedrock) database can be assembled from the literature. For most archaeological problems, a whole‐rock bedrock database is more likely to exist than a mineral database, and whole‐rock analyses on artefacts will generally be easier to obtain than mineral analyses. Whole‐rock fingerprinting may be more sensitive than mineral‐based fingerprinting. Thus, if sample quantity is not an issue, whole‐rock analysis may have a slight cost, convenience, and technical advantage over mineral‐based methods. Our results also emphasize that the Egyptians cherished their Haddadin basalt flow and used it extensively and exclusively for manufacturing basalt vessels and paving stones for at least 600 years (∼3150 B.C. to 2500 B.C., approximate ages of the vessels and Abu Sir paving stones, respectively). © 2001 John Wiley & Sons, Inc.     

Four Natural Chromite Reference Materials for the Determination of the First-Row Transition Elements and Gallium by LA-ICP-MS

Four natural chromite samples (LBS13-04, LBS13-06 and LBS13-13) from the Luobusa ophiolite (China) and 16SW2-6 from the Stillwater Complex (USA) were developed as reference materials for in situ element microanalysis. Approximately 8 g of chromite fragments with grain sizes of 0.5–1.5 mm from each chromite sample were separated under a binocular microscope and analysed by EPMA, XRF, LA-ICP-MS and solution nebulisation ICP-MS techniques for major and trace elements at six laboratories. The results show that the four chromite samples are homogeneous with respect to MgO, Al₂O₃, Cr₂O₃, FeO, Sc, Ti, V, Mn, Co, Ni, Zn and Ga. These samples are thus suitable to be used as reference materials for in situ microanalysis.     

An Optimised 1,10‐Phenanthroline Method for the Determination of Ferrous and Ferric Oxides in Silicate Rocks,Soils and Minerals

A precise, accurate and rapid method for the sequential determination of FeO and Fe₂O₃ in rocks, soils and some non‐refractory minerals by 1,10‐phenanthroline spectrophotometry is described. Fe(II) and Fe(III) were leached from the sample (?200 mesh) using a mixture of NH₄HF₂ and H₂SO₄ at 40–80 °C for 10 min on a hot plate. Both Fe(II) and Fe(III) could be conveniently estimated sequentially from the same reaction mixture at the μg g^?1 to percentage level. The method is better than the existing wet chemical methods, including the commonly used Pratt's titrimetric redox method, for Fe(II) and Fe(III) determinations in rock and soil samples in terms of precision, accuracy and rapidity. The throughput of the method was very high; at least forty to fifty samples could be estimated easily in a day. The results obtained compare favourably with those obtained by Pratt's method, as well as for certified/recommended values of a set of eleven certified reference materials having FeO and Fe₂O₃ contents in the range 0.21–14.63% and 0.58–8.48%, respectively. The optimised 1,10 phenanthroline method was found to be accurate to within 0.21% m/m FeO and 0.30% m/m Fe₂O₃ compared with the literature values of the certified reference materials studied.     

山东省济阳县土壤重金属元素异常成因研究

基于山东省济阳县土壤地球化学调查数据,发现济阳县城北部农田区有As、Bi、Cd、Cu、F、Ni、Sb、Hg、Zn等重金属为主的元素异常,各元素异常套合较好,异常衬度相差较大,呈弱富集状态。异常查证结果表明,重金属元素含量与SiO2、Al2O3、Fe2O3等常量组分之间具有显著的相关性,随SiO2含量的增加而降低,随Al2O3、Fe2O3含量的增加而增加,说明土壤常量组分及其所决定的土壤质地是导致异常形成的主要因素,而人类活动的后期叠加作用是异常形成的次要因素。在异常区所抽检的小麦、黄瓜样品中,Hg、F等元素有不同程度超标现象,说明异常区土壤中有毒、有害元素已对农产品质量产生影响,应引起重视。科学合理施肥,加强各类污染源的控制,继续保持土壤碱性环境,是防止异常区危害人类健康的有效措施。