中国煤中氟的环境地球化学研究

氟是煤中含量较高的微量元素，大多在20-500mg／kg，平均值为150mg／kg左右。煤在燃烧时，其中的氟化物将发生分解，大部分以日F、SiF_4等气态污染物形式排入大气，不仅严重腐蚀锅炉和烟气净化设备，而且造成大气氟污染和生态环境的破坏。氟是人体所必需的微量元素，但摄入过量则会催患氟斑牙和氟骨症。燃煤污染型氟中毒为我国所独有，导致了近1500万患者，这是人类有史以来最严重的环境污染导致的健康危害事件。因此，根据目前国内外对煤咔l氟的研究进展，研究中国煤中氟的含量、分布及其影响因素；燃煤型氟中毒的环境地球化学特征；选煤脱氟的机理；粮食中氟的分析方法既有理论意义又有现实价值。通过本文的研究，得出以下几点认识：1、通过在全国有计划的系统取样。统一采用当前最有效的分析方法-高温热水解-离子选择性电极法来获得中国煤炭的平均氟含量。与世界煤相比，中国煤含氟量正常，绝大部分（90％）煤的含氟范围为47～347mg／kg，全国煤 氟平均含量为136mg／kg。澄清了长期以来关于中国煤炭高氟的错误认识，为正确计算燃煤的氟排放通量并评价其环境影响提供了较准确的基础资料。2、中国煤中氟含量与灰分显著正相关，表明煤中氟主要以无机矿物形式赋存。3、在本批样品中按变质程度的不同，煤含氟量由低到高依次为贫煤、长焰煤、无烟煤、气煤、焦煤、肥煤、瘦煤和褐煤。煤中的氟主要赋存于无机矿物中，以无机形态赋存的氟不受煤变质程度的影响。从褐煤到无烟煤，煤中的氟含量和煤变质程度之间没有必然的关系，在讨论煤氟含量与变质程度的关系时要考虑氟的赋存形态的影响，以统计分析的方法来研究其间的相互关系时要慎下结论，某些变化趋势不一定就是必然的规律。4、在本批样品中按地质时代的不同，煤中氟含量由低到高依次为早石炭世、中侏罗世、早侏罗世、早二叠世、晚石炭世、中石炭一世、晚侏罗世、第三纪和晚三叠世。煤中的氟含量受物质来源、成煤环境、后期地质地球化学作用等多种因素的影响，而我国幅员辽阔、成煤期多、煤田分布广，而且同地质时代的不同煤矿区（或者地质单元）可以具有相同条件，也可具有不同条件，致使影响含氟量的各种因素大多只具有局部性，造成成煤时代等单一因素的作用可能为其它各种因素的作用所掩盖，对此有必要进行更深入具体的研究。5、拌煤的粘土取自土壤的淀积层，其氟含量非常高。中国煤氟的含量不高，远低于淀积层粘土的氟含量。在燃煤型氟中毒病区通常用粉煤与粘土加水搅拌制成湿的煤泥在无烟囱的炉灶内燃烧。使用烟煤和无烟煤的燃煤型氟病区的氟主要来自于拌煤的粘土。我们突破了长期以来关于氟源是高氟煤的错误认识，这为正确、有效地防治燃煤型地氟病提供了新的思路。6、在石煤污染型氟病区石煤的风化淋溶对水环境、粮食作物的含氟量影响不大，但其燃烧后释放出的的气态、气溶胶态和尘态氟会污染室内空气、粮食、蔬菜和饮水从而导致人体摄氟过量而中毒。改良炉灶，改变在厨房烘烤、存放辣椒的陋习，经常清扫室内，尤其是室内上部灰尘，防止灰尘坠落污染食物、饮水等，对．预防氟中毒有重要意义。7、选煤可降低灰分、硫分，同时还能有效脱除煤中的氟及其他有害微量元素，从而可减少运输成本，降低粉煤灰的收集、处理和处置与有害微量元素的排放控制费用，提高燃烧热效率，符合以预防为主的国家环保政策，要大力倡导。8、我们采集的病区玉米第二次酸浸时浸出液含氟量低于检测限；而辣椒由于含油较多，辣椒油阻碍了氟的浸出，这导致浸泡两、三次后在浸出液中还能检测出氟。在地氟病区采用酸浸一离子选择性电极法测定氟含量时，玉米浸泡一次即可满足研究需要，而对于辣椒则宜进行多次浸泡。一次或多次未浸出的氟含量基本为一个定值，在研究地氟病时不用对此作太多考虑，但在制订粮食的含氟量及人体的摄氟量标准时要将这一部分氟考虑进去。

贵阳市表层土壤重金属污染元素环境地球化学基线研究

贵阳市位于贵州省中部云贵高原东斜坡地带，地处东经106°07′至107°17′，北纬262°11′，至272°22′之间，属东部平原向西部高原的过渡地带，地形地貌多样，海拔高，纬度低，具有亚热带湿润温和型气候的特点，资源丰富，能源充足，自然环境得天独厚。本论文详细研究了贵阳市8046平方公里面积内表层土壤中砷、福、铬、铜、汞、镍、铅、锌8种重金属污染元素的环境地球化学特征，确定了土壤环境地球化学基线，并建立了判别自然的和人为的环境影响的地球化学指标，进而计算污染参数：重金属累计指数和污染程度，在此基础上进行了土壤重金属污染来源分析。取得认识如下：1、贵阳市表层土壤中重金属污染元素的均值、标准差、极值、主要含量区间分别是：砷18·ogmg／kg、11·57 mg／kg、79.30mg/kg、AS95.9％＜40mg/kg；福0.302mg／kg、0.363mg／kg、2.620mg／lcg、Cd95.7％＜1.000mg／kg；铬75.3mg／kg、37.3mg／kg、271.0mg／kg、Cr95.9％＜150.0mg／1cg；铜43．lmg／kg、30.3mg/kg、213.0mg瓜g，Cu94.6o／＜100mg／kg；铅43.2mg／kg、31.3mg／kg、318.9mg/kg，Pb95.5％＜100.0mg/kg；汞0.222mg／kg、0.531mg／kg、7.030mg／kg，Hg98.2％＜1.00Omg/kg；镍38.3mg/kg、14.9mg／kg、102.5mh/kg，Ni95.8%＜70mg/kg；锌84.7mkg、49.8mg／kg、385.0mg/kg，Zn93.4％＜150.0mg/kg。2、利用相对累计总量分析方法和相对累计频率分析方法确定贵阳市表层土壤中重金属元素的基线值和受人为影响的下限：砷为9.04mk和29.0mg/kg；福为0.068mg／kg和1 ．OIOms／kg；铬为44.0mg／kg和100.2mg/kg；铜为18.8mg/kg和68.4mg/kg；铅为14.8mg/kg和70.lmg／kg；汞为0.045mg／kg和0.530mkg；镍为17.0mg/kg和57.0mg/kg；锌46.3mg/kg和112.0mg/kg。3、对贵阳市表层土壤重金属含量进行地质累计指数分析，结果显示贵阳市的表层土壤中：41％未受砷污染，43％的在无污染到中度污染之间，14％的中度污染，只有2％的介于中度污染到强污染之间；40％未受福污染，19％无污染到中度污染之间，14％的中度污染，19％的介于中度污染到强污染之间，7％的强污染，1％的表层土壤强污染到极强污染之间；46％未受铬污染，47％在无污染到中度污染之间，6.8％的中度污染，0.2％介于中度污染到强污染之间；38％未受铜污染，38％在无污染到中度污染之间，22％的中度污染，2％的介于中度污染到强污染之间；18％未受铅污染，47％在无污染到中度污染之间，28％的中度污染，3％介于中度污染到强污染之间；12％未受元素汞污染，37％在无污染到中度污染之间，36％的中度污染，11％介于中度污染到强污染之间，2％的强污染，1％的介于强污染与极强污染之间，1％的极强污染；19.2％未受镍污染，63.7％在无污染到中度污染之间，16.8％的中度污染，0.3％介于中度污染到强污染之间；41％未受锌污染，50％在无污染到中度污染之间，7％的中度污染，2％介于中度污染到强污染之间。4、贵阳市表层土壤中重金属元素含量的污染程度计算显示：砷的污染程度最大为4，27，50.2％的表层土壤未受污染，97％的表层土壤污染程度小于2，总污染程度略大于O，即受到轻微污染；蝠的污染程度最大为12.1，57.9％的表层土壤未受污染，％％的表层土壤污染程度小于4，总污染程度大于。，即受到污染；铬的污染程度最大为2.01，69％的表层土壤未受到重金属元素铬的污染，30.6％的表层土壤受到轻微污染，总污染程度小于O，即未受到污染；铜的污染程度最大为5.09，53.2％的表层土壤未受到重金属元素铜的污染，总污染程度略大于0，即受到轻微污染；铅的污染程度最大为8.11，49.9％的表层土壤未受到重金属元素铅的污染，总污染程度略大于0，即受到轻微污染；汞的污染程度最大为45.87，56.1％的表层土壤未受到重金属元 素汞的污染。总污染程度大于0，即受到污染；镍的污染程度最大为1.56，64％的表层土壤未受到重金属元素镍的污染，总污染程度小于O，即未受到污染；锌的污染程度最大为2.85，77.8％的表层土壤未受到重金属元素锌的污染，总污染程度小于0，即未受到污染。综合考虑8种重金属污染元素，贵阳市40.2％的表层土壤无重金属元素污染，巧％的表层土壤在无污染到轻微污染之间，36.1的表层土壤轻微污染，7.2％的中度污染，1.4％的表层土壤严重污染。5、福和镍只存在较少的污染区域，其余六种元素都存在局部的重金属含量受人为因素影响。砷的污染区域主要集中在筑东部的马场和西部清镇的暗流、王家院等地；铬的污染区域主要集中筑南部的花溪马林、西部的暗流一酒坪等地；铜的污染区域则主要集中在筑南部的燕楼马林处；汞的污染区域分布在筑北开阳双流、筑西北六广以及筑中扎佐三片；铅的污染区域分布在筑东北的宅吉、城关；筑西麦格等处；而锌的污染区则集中在筑东北面的开阳花梨和城关。总体来说，镍、铜的含量是处于最安全的位置，而汞、铅的警戒区域面积很大，几乎函盖了全部研究区域，福次之，砷、锌、铬适中。6、贵阳市表层土壤中重金属污染元素的含量主要与矿山、长期的农业措施和燃煤带来的污染有关。所有重金属含量超标区几乎都对应于矿区，其污染可能来自于母岩，也可能来自矿区生产而导致的“三废”污染。汞、铅、镉的“警戒”区域面积较大，主要是由长期的农业污染造成，特别是磷肥和含污染元素的农药、除草剂等的施用，汞、隔“警戒”区域面积较大的原因还与燃煤后重金属的大气沉降有关。另外砷的污染也和燃煤后大气沉降有关。贵阳市表层土壤没有受到重金属污染元镍的污染。7、在本研究区域内，重金属含量呈现不同含量等级的土类是由于长时间受人为影响的结果，而重金属含量处于单一等级区间的土类则受人为因素影响较小，其含量区间反映了背景值含量范围。在贵阳市的表层土壤中，黄壤、石灰土、水稻土受人为影响较多，石质土、粗骨土、紫色土、黄棕壤受人为影响适中，沼泽土和山地草甸土受人为影响较少。8、本文建议：（1）在乌当区金华镇三铺村、修文县久长镇新隆村、白云区牛场乡小山村、修文县扎佐镇丁官村、修文县大石乡天桥村、开阳县双流镇凉水井村、修文县六广镇滨江村这几个综合污染较为严重的区域采取政府宏观调控手段，指导当地农户进行绿化苗木、花卉等不进入食物链的植物，或者在合适的地方，进行退耕还林，种植生态林。同时建议有关部门在这些区域开展土壤重金属治理工作；（2）在清镇市的暗流一卫城、王家院、水塘以及开阳县马场一哨上等砷含量较高区域种植旱生禾谷类食用籽粒的作物，如小麦、玉米、高粱等，不能种植水生作物和叶菜类作物；在北部开阳双流片、西北部修文六广一大石片、筑中扎佐一牛场片汞含量较高区域推广竺麻的种植；在东北部开阳花梨一城关锌含量较高区域建议农户种植玉米；在开阳的宅吉一龙水、城关和清镇的麦格片区铅含量较高区域，大力发展烟草的种植；在修文久长、大石、开阳城关一马场、清镇麦格、乌当水田一新堡等搞含量较高地区推荐种植豆科食用籽粒作物。9、综合考虑国家《土壤环境质量标准（GB15618一1995）》中规定监测的8种重金属污染元素，污染程度（Cd）的判别指标可以定量化为：Cd≤O：无污染；O＜Cd燕1无污染到轻微污染；1＜Cd≤5：轻微污染：5＜Cd≤10中度污染；Cd＞10：严重污染。

Strong visible up-conversion emissions and thermometric applications of Er3+-Yb3+ codoped Al2O3 prepared by the sol-gel method

The Er3+-Yb3+ codoped Al2O3 has been prepared by the sol-gel method using the aluminium isopropoxide [Al(OC3H7)(3)]-derived Al2O3 sols with addition of the erbium nitrate [Er(NO3)(3) center dot 5H(2)O] and ytterbium nitrate [Yb(NO3)(3) center dot 5H(2)O]. The phase structure, including only two crystalline types of doped Al2O3 phases, theta and gamma, was obtained for the 1 mol% Er3+ and 5 mol% Yb3+ codoped Al2O3 at the sintering temperature of 1,273 K. By a 978 nm semiconductor laser diodes excitation, the visible up-conversion emissions centered at about 523, 545, and 660 nm were obtained. The temperature dependence of the green up-conversion emissions was studied over a wide temperature range of 300-825 K, and the reasonable agreement between the calculated temperature by the fluorescence intensity ratio (FIR) theory and the measured temperature proved that Er3+-Yb3+ codoped Al2O3 plays an important role in the application of high temperature sensor.

水库滑坡复活机理及其发展趋势预测研究

Various numbers of ancient landslides of various scales are frequently distributed on both banks of reservoirs, especially large reservoirs, both in China and abroad. During inundation and operation of theses reservoirs, some of the landslides are reactivated, which caused losses of people's lives and properties to various extents, some even disasters. Systematic studies are, however, very few on the reservoir-induced reactivation mechanism and development tendency prediction. Based on investigation of reservoir-induced reactivation phenomena of ancient landslides and relevant existing research problems, a systematic study is carried out on the field identification, induced reactivation mechanism, development tendency prediction, risk decision-making and treatment of reservoir-related ancient landslides, through analysis of large numbers of engineering geological investigation results, scientific experimental and research results, in combination with prevention and treatment practices of reservoir-related landslides both in China and abroad, and a series of research results have been obtained. 1. On the basis of study of the distribution features, genesis mechanism of ancient landslides on river banks, a set of scientific methods are summarized on field identification of ancient landslides, and a significant method named "lithologic sequence method" or "indicator layer method", is proposed, which is proved to be very useful. 2. A detail study is made on the reservoir-induced hydraulic effects and material mechanic effects (or softening effects) on the ancient landslide through model and case studies, which concludes that the magnitude and properties of reservoir-induced hydraulic effects are related to the shapes of sliding planes, water content and permeability of landslide materials and variation rate and magnitude of reservoir levels; the magnitude of material mechanic effects are related to the material composition (including mineral composition and grain size), natural water content and saturation state of sliding zones. Also a sensitive analysis is made on the factors that are related to the stabilities of the landslides, which indicate that the stability of a landslide is more sensitive to the groundwater head h_w in the slides and the inner friction angleψof sliding zones than others. 3. The joint inducing mechanism of rainfall and reservoir is also discussed in the paper through model analysis and case study, which proves that reservoir inundation increases firstly the sensitivity of a landslides to rainfall through reduction of its stability or cracking deformation which will increase the rainfall infiltration to the slide body, and then rainfall triggers reactivation or intensifies the reservoir-induced deformation of a landslide. 4. Based on rheologic test results of sliding zones of several reservoir-related ancient landslides, the rheologic characteristics of sliding zones have been discussed in detail and several typical rheologic models have been set up, which well explains the dynamic process of slide deformation. The response types to reservoir inundation and development tendency of reservoir -related ancient landslide are discussed in the paper based on field investigation results. And prediction methods for reservoir-related landslides have been studied based on the Mate-Synthetic principle of quantitative and qualitative analysis, as well as combination of computation and internal mechanism analysis, and a rheologic analytical method is proposed which is proved very useful for prediction of the landslide development tendency. 6. In disaster-prevention and treatment of reservoir-related landslides, risk decision-making has been proved very significant both in engineering and economics. Based on the practices in disaster-prevention and treatment of reservoir-related landslides both in China and abroad, the disaster-prevention risk decision-making for reservoir-related landslides has been proposed in terms of philosophy, methods and procedures, and well put into practice. A summary is also made through case study of the experiences of treatment of reservoir-related landslides both in China and abroad in terms of principle, methods and technical lines. 7 A detail study is made as a case study of the reactivated Maoping ancient landslide on the left bank of the Geheyan Reservoir on Qingjiang river in Hubei province, China, including its field identification features, reservoir-induced reactivation characteristics and mechanism, development tendency prediction and proposed counter measures based on risk analysis.