重庆城口地区下寒武统黑色岩系元素地球化学特征及其成因

地区广泛发育有下寒武统。利用ICP-MS方法系统分析重庆城口地区下寒武统黑色岩系中多金属富集层、炭质粉砂岩以及硅质岩样品的微量元素、稀土元素组成。研究结果表明稀土总量为111.41×10-6~184.13×10-6,平均为138.83×10-6,相对其他地区黑色岩系较低;LREE/HREE=2.49~3.44,LREE相对富集,HREE亏损;δCe=0.39~0.46,Ce呈明显负异常;δEu=0.84~1.10,Eu异常不明显。δCe,δU,V/Cr,Ni/Cr,V/(V+Ni)表明该区黑色岩系形成于缺氧环境;稀土元素地球化学特征及其相关图解、Cr,Sb,As,Bi的富集以及U/Th等反映本区黑色岩系非正常海水沉积产物,明显受热水沉积的影响,同时还存在火山活动的影响,火山活动可能为热水活动提供了动力及物质成分。     

黔北务正道地区含铝岩系地球化学特征及地质意义

对黔北务正道地区大竹园、岩凤阡和旦坪三个铝土矿床的含铝岩系元素地球化学特征进行研究,结果表明:常量元素主要由Al_2O_3、SiO_2、Fe_2O_3、TiO_2组成,铝土矿呈富铝、低铁的特点;Zr、Sr、Cr、V、Li等微量元素含量均达到100×10~(-6)以上,尤其以元素Li含量最高;Be含量4.04×10~(-6)~7.04×10~(-6),表明铝土矿以沉积成因为主,局部地段具残积成矿的特点;Th/U介于2~7之间,揭示了铝土矿风化作用不彻底或者有沉积混杂;Sr/Ba1,表明铝土矿主要形成于海相沉积环境;V/Cr=0.90~1.112.00、Ni/Co=0.58~4.125.00、V/(V+Ni)=0.72~0.880.60,表明铝土矿主要形成于富氧的沉积环境;ΣREE值总量较高,轻稀土较富集,Eu轻微正异常、Ce明显正异常;Ce/Ce*1,表明铝土矿沉积于富氧环境;La/Yb-REE关系图解中所有样品并没有集中落在沉积岩区,表明成矿物质具有多源性。综合分析认为,本区铝土矿床为晚志留世-石炭纪形成初始矿源层,并在二叠世早期风化搬运至湖泊沼泽或近岸浅海进一步富集成矿。     

有机化合物分子体积的加和性--Ⅰ.烃类的官能团的拓扑体积

液态的碳氢化合物分子体积等于官能团拓扑体积之和,即服从于加和性原则。在不同的烃类中相同的官能团有十分接近的体积贡献。官能团的拓扑体积,V（CH₂）=27.24Å3,V（CH₃）=55.11Å₃,V（-CH=CH₂）=70.12Å3,V（-CH=CH-）=40.98Å3,V（-C≡CH）=51.58Å3,V（-C≡C-）=21.18Å3,V（H）端部=29.32Å3。V（C₆H₅-）=120.08Å3,V（-C₆H₄-）=89.92Å3,V（-C₆H₄=）=61.51Å3。液态碳氢化合物的分子体积还可以用如下公式来表示。V=k+13.89·C+6.67HÅ3）K为液体常数,烷、烯和炔K=40,苯同系物K=25,环烷烃K=15。C、H分别是分子中C和H的原子数。     

交互正交试验设计在Mn/Ce催化剂制备中的应用

利用交互正交试验设计对柠檬酸络合法制备Mn/Ce复合氧化物催化剂(简称Mn/Ce催化剂)的制备条件进行了优化,重点考察金属配比(Mn∶Ce=7∶3、1∶1、3∶7)、焙烧温度(350℃、500℃、650℃)、焙烧时间(2 h、3.5 h5、h)等3种因素对催化湿式氧化(CWAO)降解正丁酸过程中Mn/Ce催化剂活性的影响。结果表明,金属配比和焙烧温度对催化剂活性有显著影响(置信度p分别为99%和95%),焙烧时间对催化剂活性无显著影响(p=90%),焙烧温度与金属配比之间有显著的交互作用(p=99%),得到的最佳制备条件为:Mn∶Ce=3∶7、焙烧温度500℃和焙烧时间5 h;并对最佳制备条件下得到的Mn/Ce催化剂进行XRD、BET和SEM等表征。     

利用粉煤灰处理含铜废水的实验研究

研究了粉煤灰去除废水中铜离子的速率、粉煤灰投加量对粉煤灰去除废水中铜离子的影响和粉煤灰对质量浓度不同的含铜离子废水的去除效果,进一步探讨了粉煤灰去除铜离子的机理,实验结果显示粉煤灰在去除废水中铜离子的过程中反应3 h后就达到了平衡,粉煤灰对Cu2 的去除率随粉煤灰投加量的增加而增加,但是就充分利用吸附剂粉煤灰的角度而言,并非其投加量越多去除量越大,粉煤灰吸附废水中的铜离子更符合Langmuir模型,而不是Freundlich模型;粉煤灰去除废水中的Cu2 主要是静电吸附、阳离子交换吸附和表面络合吸附作用,但是,当用碱性粉煤灰处理质量浓度较低的含Cu2 废水时,生成Cu(OH)2的沉淀作用可能占主要的地位.     

碧口地块富铁硅岩REE及Nd—Sr同位素组成及其古环境意义

对碧口地块富铁硅岩进行稀土元素及同位素数据测试证实其δEu=1.02～8.79,8Ce=0.44～1.26,(La/Yb)N=0.071～1.285,除个别样品外,大部分样品同时发育程度不等的Eu正异常、Ce负异常和LREE相对亏损的特征,其稀土样式总体上与海底热水流体类似,表明富铁硅岩为热水喷流成因.富铁硅岩Y/Ho比值在22～47之间,与Ce/Ce*存在明显的负相关关系,反映二者变化受流体、海水混合过程控制.根据富铁硅岩Ce/Ce*和Y/HO的拟合方程,预测古海水端元的Ce/Ce*比值为0.55左右.富铁硅岩的Nd同位素初始比值ENd(t)为4.9～-5.1,与Ce/Yb比值呈粗略负相关关系,表明富铁硅岩稀土主要来自古海底热水流体和海水两个端元.87Sr/86Sr比值0.710 053～0.717 020,不仅高于对应同时代地幔Sr比值,也较新元古代海水畜放射Sr,表明形成富铁硅岩海水以高放射Sr为特征.结合古海水的Ce负异常和高放射Sr的特征,推断富铁硅岩形成于陆缘到深海盆地之间的过渡位置.     

四川广元-陕西镇巴地区上奥陶统五峰组地球化学特征及沉积环境意义

上奥陶统五峰组黑色页岩有机质含量高,生烃潜力巨大,为南方海相油气勘探的重点层位。对于上奥陶统五峰组的沉积环境,历来争议较大,主要为浅水成因论和深海成因论。本文从前人的研究成果出发,运用元素地球化学方法,对研究区五峰组的古氧相、古气候、古水深等沉积环境进行分析。分析结果显示,研究区V/(V+Ni)平均值为0.64;U/Th为1.87;V/Cr为2.98;Ni/Co为15.07,V/(V+Ni)、V/Cr、U/Th等值均指示研究区五峰组沉积环境为强还原环境。Mn O/Ti O2比值在0.02~1.89之间,其平均值为0.23,指示离陆地较近的边缘浅海环境;样品总体上表现为高Ba低Sr的趋势,Sr/Ba比值普遍较低,平均值为0.02,远远小于1,指示五峰组沉积环境应该为淡水沉积。稀土元素总体表现为轻稀土富集,δCe值位于0.77~1.57之间,平均值为1.11,为Ce正异常或不明显的Ce负异常,Ce/La平均值为2.22,δEu平均值为0.59,表明研究区五峰组形成于贫氧-厌氧的浅海沉积环境。     

新矿物丁道衡矿-（Ce）：珀硅钛铈矿的同质多象体和硅钛铈矿亚族C（1）位上的钛类似矿物

丁道衡矿-(Ce):(Ce,La)4Fe2 (Ti,Fe2 ,Mg,Fe3 )2Ti2Si4O22,理想的结构化学式Ce2Ce2Fe2 Ti2Ti2Si4O22单斜晶系,α=1.34656(15)nm,b=0.57356(6)nm,c=1.10977(12)nm,β=100.636(2)°,V=0.84239(46)nm3,空间群P21/a(假C2/m),Z=2.作为硅钛铈矿(chevkinite)族矿物的新成员,它产于举世闻名的白云鄂博铁.稀土.铌矿床镁夕卡岩中,多数单晶体长0.2～1.0 cm,最大者长大于1.5 cm.共生矿物有透辉石、透闪石、钠透闪石、褐帘石-(Ce)、磁铁矿、尖晶石、烧绿石、氟金云母、氟磷灰石、石英和萤石等.矿物具有褐色条痕和半金属一金属光泽的黑色,其褐黑色碎片半透明.性脆、具有贝壳状断口、无解理和裂开.显微硬度(VHN25g)为606.0～717.4 kg/mm/12(相当于摩氏硬度约5.9).矿物实测密度4.83(7)g/cm3,计算密度值4.88(0)g/cm3.丁道衡矿-(ce)的反射色为带灰色的浅黄色,多色性为不同色调的灰色.平均反射率(λ=589nm)为11.4%～12.5%.矿物为二轴晶负光性.作过结构精测的丁道衡矿-(Ce)晶体的电子探针测值:SiO2:19.29,TiO2:18.26,A12O3:0.04,FeO:8.49,Fe2O3,:1.67,ThO2:0.16,MgO:1.32,CaO:2.17,Nb2O5:0.47,Ta2O5:0.00,La2O3:19.53,Ce2O3:28.08,Y2O3:0.00,Na1O:0.01,总量99.46%;其中Fe3 /Fe2 的比值依穆斯堡尔谱换算.根据结构精测每个单位分子式中O=22和C(1)位上Ti优先占位,计算的矿物晶体化学式为(Ce2.13,La1.49Ca0.48Th0 01)Σ4.11Fe2 (Tin0.88Fe2 0.47Mg0.41 Fe0.0)Σ2.03(Ti1.96Nb0 04)Σ2.00(Si2O7)2O3.分别用P21/a和C2/m对丁道衡矿-(Ce)的晶体结构作了精测.结果表明,丁道衡矿-(Ce)的真空间群是P20/a.换言之,它才是真正珀硅钛铈矿[perrierite-(Ce)]的同质多象体.显而易见,硅钛铈矿族矿物既可以有P21/a空间群,又可以有C2/m空间群.     

陕西南郑马元铅锌矿区灯影组白云岩地球化学特征

灯影组白云岩是南郑县马元铅锌矿的赋矿围岩。本文通过野外调研和主、微量及稀土元素的分析研究,探讨了赋矿围岩白云岩的沉积环境。白云岩主量元素CaO为23.15%~30.54%,MgO为16.53%~22.05%,SiO2为0.43%~26.06%,钙镁含量及比值都接近纯白云岩(CaO为30.4%,MgO为21.8%,CaO/MgO=1.39)的值,表明灯影组地层主要为白云岩。Al2O3、K2O、Fe2O3、TiO2含量极低,表明灯影组白云岩基本不受陆源组分的影响。因此,利用微量、稀土元素判别沉积环境是可靠的。白云岩微量元素V/Cr、Ni/Co、V/(V+Ni)比值分别小于2、5、0.6,U/Th比值介于1.89~230.00,均值75.24,后太古代页岩标准化后稀土元素具有中稀土富集、轻稀土与重稀土相当、正Eu异常及正Ce异常的特征。V/Cr、Ni/Co、V/(V+Ni)比值及正Ce异常表明灯影组白云岩沉积时水体处于氧化环境,异常高的U/Th比值及正Eu异常暗示灯影组白云岩沉积时水体受海底喷流热卤水的影响。     

西南天山马达尔地区硅质岩地球化学特征及其沉积环境

西南天山马达尔地区乌帕塔尔坎群硅质岩与玄武岩以逆冲断层接触产出,但其时代缺乏依据。本次研究的硅质岩中含有放射虫,经鉴定时代为D3—C1。11件硅质岩样品的SiO2含量为88.80%～93.28%,Al2O3含量为2.02%～3.72%,其中只有4件样品为纯硅质岩(SiO2的含量为91.0%～99.8%),所有样品的SiO2/Al2O3值(23.84～46.11)远低于纯硅质岩(SiO2/Al2O3=80～1400),表明其含有较高比例的陆源泥质沉积物。Al/(Al+Fe+Mn)=0.57～0.72,Ce/Ce*=0.90～1.21,显示出生物沉积硅质岩的特点。此外,其Al2O3/(Al2O3+Fe2O3)=0.64～0.77,V含量为10.92×10-6～26.70×10-6,Cu含量为2.15×10-6～34.10×10-6,Ti/V=25.53～44.93,∑REE为30.78×10-6～59.26×10-6,平均值为45.46×10-6,(La/Yb)N=0.88～1.33,平均值为1.09,(La/Ce)N=0.81～1.12,介于洋盆沉积物和大陆边缘沉积物之间,反映其沉积环境为接近陆源的深水-半深水的沉积环境。Ceanom值均大于-0.1,为-0.06～0.08,并且出现Eu的负异常,推测岩石沉积时水体贫氧。结合区域地质特征推测,乌帕塔尔坎群硅质岩形成于南天山洋盆闭合期的小洋盆。     

含氟废水的粉煤灰处理实验研究

进行了影响粉煤灰处理含氟废水的各种条件实验，（pH、水灰比、氟浓度、振荡平衡时间），结果表明最佳处理条件是pH值为2．5、水灰比为小于20、氟浓度小于500mg/l、振荡平衡时间大于2．5h，并研究了粉煤灰处理含氟废水的机理，给出了其吸附等温式。     

Morphological Dynamics of the Rivers of Brahmaputra

The Singrauli region is known for fluoride contamination and its effect on human population. In this work the possible sources of fluoride contamination in Rihand reservoir water is constrained. They include slurry water, fly ash and coal samples of various thermal power plants, coal seams and granites of the region. Petrographic study depicted the presence of fluoride bearing minerals - flour apatite in pink granite. Preliminary scanning electron microscope studies revealed presence of fluorine peak in coal samples. The chemical analysis confirmed the presence of fluoride in fly ash (12.6 mg/kg), drain water (5.34 mg/l), soil (6.1 mg/kg), coal (3.1 mg/kg). They confirmed the source of fluoride from coal of thermal power plant which utilized coal from Singrauli coal seam (1.6 mg/kg). Further the Rihand reservoir water is also enriched by fluoride contaminant (upto 4.7 mg/l). This contaminates groundwater of the area as well. The contaminated water used for drinking and agriculture affects health of inhabitants in the area. It is concluded that the main source of fluoride contamination in the study area is due to coal burnt in thermal power plant and pink granite formation of the area, both anthropogenic and geogenic sources are implied.     

Adsorptive removal of pharmaceuticals and personal care products from aqueous solutions by chemically treated fly ash

This study investigated the removal efficiency of pharmaceuticals from aqueous solutions supported on chemically treated fly ash. The coal fly ash was supplied by the electric power station in Krakow, Poland. There are plenty of studies showing the utilization of fly ash as a low-cost adsorbent for wastewater containing heavy metals or dyes. Adsorption and immobilization of pharmaceuticals and personal care products on fly ash is a relatively new method but it is a very promising one. In this study, the adsorptive removal of diclofenac, ketoprofen, carbamazepine, bezafibrate, bisphenol A, 17α-ethinyl estradiol and estriol by HCl- and NaOH-treated fly ash was assessed. Chemical treatment of fly ash changed structures of particles and enhanced specific surface areas. HCl-treated fly ash was characterized by the highest BET specific surface area 47.9 m² g^?1 and unburned carbon content 8.1%. Isotherms for all compounds except for 17α-ethinyl estradiol (EE2) and estriol (E3) were linear. Higher linear regression coefficients (R ²) obtained for isotherms of EE2 and E3 show that the Freundlich model better describes their sorption. Adsorption coefficients K _d varied between 109.5 (L kg^?1) for bisphenol A and 471.5 (L kg^?1) for bezafibrate. Freundlich constants (K _F) for EE2 and E3 were 62.3 and 119.9 (µg^1?1/n L^1/n kg^?1), respectively. Acid treatment of fly ash increased adsorption of diclofenac, ketoprofen, carbamazepine, bezafibrate and bisphenol A. Comparison of the octanol–water partitioning coefficients (log K _OW) with the partitioning coefficients normalized on unburned carbon content (log K _UC) revealed similarities but no strong correlation. The increasing of unburned carbon increased sorption of compounds to fly ash.     

垃圾焚烧飞灰水泥固化体强度稳定性研究

针对垃圾焚烧飞灰安全处置技术要求,采用水泥对其进行固化、稳定化处理,研究了不同水泥添加量、不同养护时间和渗沥液浸泡时间对固化体无侧限抗压强度及破坏特性的影响,并对垃圾渗沥液的侵蚀机制进行了分析。结果表明：当水泥添加量小于5%,养护时间小于3 d时,飞灰固化体在渗沥液浸泡下迅速解体,垃圾渗沥液的侵蚀对飞灰固化体的强度有较大的影响,浸泡后的固化体呈现出明显的应变软化特征,而未经浸泡的固化体的强度增长符合y=a[1-exp(-bt)]模式。随着水泥添加量及养护时间的增加,飞灰固化体无侧限抗压强度增加,破坏应变减小,而随着浸泡时间的增加,飞灰固化体的无侧限抗压强度先增大后减小,转折点大约在5～7 d,破坏应变近似呈线性增大。渗沥液对飞灰固化体的侵蚀主要是其成分抑制了固化体水化反应和破坏了水化产物。研究成果可为垃圾焚烧飞灰的安全处置技术提供理论依据和参数支持。     

Impact of co-combustion of petroleum coke and coal on fly ash quality: Case study of a Western Kentucky power plant

Petroleum coke has been used as a supplement or replacement for coal in pulverized-fuel combustion. At a 444-MW western Kentucky power station, the combustion of nearly 60% petroleum coke with moderate- to high-sulfur Illinois Basin coal produces fly ash with nearly 50% uncombusted petroleum coke and large amounts of V and Ni when compared to fly ash from strictly pulverized coal burns. Partitioning of the V and Ni, known from other studies to be concentrated in petroleum coke, was noted. However, the distribution of V and Ni does not directly correspond to the amount of uncombusted petroleum coke in the fly ash. Vanadium and Ni are preferentially associated with the finer, higher surface area fly ash fractions captured at lower flue gas temperatures. The presence of uncombusted petroleum coke in the fly ash doubles the amount of ash to be disposed, makes the fly ash unmarketable because of the high C content, and would lead to higher than typical (compared to other fly ashes in the region) concentrations of V and Ni in the fly ash even if the petroleum coke C could be beneficiated from the fly ash. Further studies of co-combustion ashes are necessary in order to understand their behavior in disposal.     

A geochemistry study of arsenic speciation in overburden from Mae Moh Lignite Mine, Lampang, Thailand

The aim of this study was to investigate the geochemical characteristics of arsenic in the solid material samples of the Mae Moh Mine and also the Mae Moh power plants fly ash samples were systematically studied. Arsenic concentration in overburden, coal lignite and fly ash are variable (depending on source of solid samples). The results show that the strata of overburden, J seam of coal and fly ash are rich in arsenic and also relatively soluble from fly ash; it occurs as a surface precipitate on the ash particle. The experimental study on speciation in the strata also indicates that the arsenic speciation of Mae Moh solid samples are mainly arsenate, As (V), which are approaching exceed 80%. Arsenic content in the main of overburden is in the range of 14.3–888.8 mg/kg, which is larger than the arsenic background soil values. Solid materials polluted wastewater; the arsenic speciation was present predominantly as arsenate in the surface water of a series of Mae Moh solid materials basins.     

Strontium isotopes as tracers of airborne fly ash from coal-fired power plants

Fly ash generated by coal-fired power plants is in part collected by filters in the emission stacks while a small portion is vented into the atmosphere. Since many of the coalfired power plants in the western United States are located in the desnrt, the ability to monitor fly ash emissions requires a chemical tracer that utilizes desert soil and plant interactions with the fly ash deposited in the desert environment. This investigation presents the results of a controlled greenhouse experiment in which a native desert plant, the brittlebush (Encelia farinosa), was grown on admixtures of desert soils and fly ash. The fly ash is strongly enriched in Sr and the brittlebush is a Sr accumulator. The data demonstrate that (1) the brittlebush isotopically equilibrates with desert soils whose fly ash components are as low as 0.25% by weight, (2) the fly ash Sr is apparently more available to the plant, than Sr derived from the soils, and (3) the difference between the⁸⁷Sr/⁸⁶Sr ratio of the fly ash (0.70807) and soils (0.71097 to 0.71117) warrants further investigations in the natural environment to determine the practicality of this method as a natural tracer of fly ash in the environment.     

Mineralogical speciation of elements in an eastern Canadian feed coal and their combustion residues from a Canadian power plant

Systematic changes in mineralogy, enrichment and depletion of selected elements, and mineralogical speciation of selected elements in fly ash and bottom ash samples from the Lingan Power Plant were compared to run-of-mine and pulverized feed coal from the Sydney coalfield, Nova Scotia, eastern Canada. The analytical techniques used were an electron microprobe equipped with energy and wavelength X-ray dispersive spectrometers, X-ray diffraction, neutron activation, scanning electron microscopy with energy dispersive X-ray and incident light petrography. Three types of glasses (Fe/O-rich, Fe/Al/Si/O-rich and or Al/Si/O-rich) were identified in the combustion residues; they were formed as a result of the interaction of melted pyrite and clay minerals. Compared to the feed coal, most elements were enriched 10 to20 times in the fly ash. The concentration of the elements in both the fly ash and bottom ash are comparable to coal ash that is generated by the low temperature asher in the laboratory. Some chalcophile elements such as arsenic and lead occurred as a solid solution in pyrite in the feed coal and were concentrated in the float fraction (density: <2.81 g/cm³) of the fly ash with non-crystalline Fe-oxides. X-ray mapping of arsenic in the fly ash and bottom ash indicates that arsenic was evenly distributed as oxide within the Fe/O- and Fe/Al/Si/O-rich glass and crystalline phases in the fly ash, possibly in solid solution. Arsenic is associated with Fe/O and Fe/S crystalline phases in the bottom ash.     

Self-sealing isolation and immobilization: a geochemical approach to solve the environmental problem of waste acidic jarosite

Mimicking geochemical processes to solve environmental problems was implemented in dealing with waste acidic jarosite and alkaline coal fly ash. By placing these two chemically different materials adjacent to one another, a self-sealing layer was formed at the interface between both wastes, isolating and immobilizing chemical constituents in the process. A series of leaching experiments were performed on each material separately to study the release behavior of the principal constituents. Radiotracer experiments were conducted to explore diffusion and reaction of constituents such as Fe³⁺ in a combined jarosite/fly ash system. A model has been developed to simulate the coupled processes of diffusion and precipitation taking into account porosity change due to pore filling by precipitates. The formation of a self-sealing isolation layer in a hypothetical jarosite/fly ash disposal site was modelled. Leaching results indicate that the release of elements from jarosite is much larger than that from fly ash, and that the highly pH dependent release of Fe, Al, and Zn was controlled by the solubility of their hydroxides. Leaching results also suggest that precipitation reactions can be expected to occur at the interface between jarosite and alkaline coal fly ash where a large pH gradient exists. Radiotracer experiments showed that accumulation of constituents occurred at the interface. Modeled Fe³⁺ profiles in layered jarosite/fly ash were well validated by experiments. Modeling results also showed that with the accumulation of constituents at the interface, a new layer with low porosity was formed. Application of this model suggests that there is a potential use to form a self-sealing layer in jarosite/fly ash co-disposal sites.     

粉煤灰-粉质粘土对氟离子的吸附作用

不同土层对氟离子的吸附能力不同,在吸附能力较弱的土层建设贮灰场,会导致周边地下水中氟离子质量浓度较高,污染地下水。吉林市来发屯灰场运行多年来,地下水中氟离子质量浓度与背景环境未见明显差异,本文通过对来发屯灰场粉煤灰-粉质粘土和灰场外土层的比较分析,探究吸附机理,结果表明：粉煤灰-粉质粘土对氟离子有较强的吸附能力,能有效防止其对地下水的污染。