燃煤电厂废弃物中的砷对周围环境的影响

通过对电厂的煤、除尘器飞灰、渣、烟囱排放的不同粒度的细小飞灰中的砷进行分析对比，并对煤、除尘器飞灰和渣进行淋滤实验研究发现。砷在飞灰中富集，在渣中亏损，并且在细小飞灰中明显富集，20μm以下的飞灰中分布均匀。煤和渣中的砷有一定的迁移性，飞灰中的砷相对迁移性低，煤中部分砷与铁锰氧化物相关，飞灰和渣中的砷主要与碳酸盐及表面氧化物离子相关，还有部分易进行离子交换，在酸性甚至中性务件下，飞灰和渣中的砷与周围的水等介质可以部分发生交换从而进入环境。煤中约有三分之一的砷会直接挥发入空气中，随烟气排放的细小飞灰中砷明显富集且其中的相当一部分是2．5μm以下的颗粒，对大气环境及人体的潜在影响不容忽视，适当的措施减少砷的排放量很有必要。     

砷的植物修复研究进展

由于砷的毒性和"三致"效应,砷已成为人们普遍关注的环境污染之一.文章总结了砷在土壤和砷超富集植物中的形态、砷污染条件下超富集植物的生长、砷污染的植物修复以及植物超富集砷的相关机理和分子生物学研究进展.文章就砷的植物修复研究做了展望:寻找、筛选更多砷超富集植物;深入研究砷超富集机理;砷富集相关基因识别和克隆;砷超富集植物应用研究;砷超富集植物用于环境修复工程时的环境影响评价;砷超富集植物后处置与资源化技术开发.     

高砷地下水的反向地球化学模拟:以中国吉林砷中毒病区为例

饮水型砷中毒分布在中国台湾、新疆、内蒙、山西、吉林等地。笔者采用GIS的空间数据叠加技术、化验测试与环境模拟技术,进行了地下水砷的反向地球化学模拟研究。研究表明,受构造运动控制,低洼地带堆积了巨厚的粉砂淤泥质沉积物和富含有机质的湖积物,为砷的赋存提供了空间。地下水砷的富集受水中Fe、Mn、pH、Cl-、PO34-、HCO3-、SO24-、Se的影响,其中,重碳酸钙型水中砷含量最低,氯化物重碳酸钠型水砷含量最高。臭葱石(FeAsO4:2H2O)等含铁、含锰矿物在进入地下水的溶解过程中,形成铁(锰)氧化物和砷化合物(砷酸盐或亚砷酸盐)。随着Eh降低,氧化物被还原形成更为活泼的离子组分,吸附在氧化物表面的砷化合物随之解吸,还原环境有利于砷从沉积物中向水中溶解、迁移。研究结果为实施安全供水提供了重要依据。     

富砷地下水研究进展

原生高砷地下水已对人类健康构成了极大威胁，许多国家和地区对此进行了较深入的研究。在阅读国内外大量文献资料的基础上，全面系统地总结了世界范围内原生高砷地下水概况、砷富集环境和砷来源、分析方法和技术、砷富集机理以及高砷区水源安全保障技术等。提出了高砷地下水研究的主要发展方向，包括：含水介质中砷形态研究、微生物影响下含水层中砷的释放研究、同位素技术在高砷地下水研究中的应用以及高砷饮用水安全保障技术研究等。     

贵德盆地三河流域高砷地下水中溶解性有机物三维荧光特性及其指示意义

溶解性有机物(dissolved organic matter, DOM)可以通过多种方式控制含水层中砷的迁移转化。贵德盆地承压含水层地下水砷含量显著高于潜水含水层。为查明承压水中溶解性有机物对砷浓度的影响,对研究区地表水、潜水以及承压水进行吸光度和三维荧光光谱的分析,利用平行因子分析法确定了水样中有机物成分及荧光特征。结果表明,贵德盆地水体中DOM包含陆源类腐殖质(C1)、受人为影响的腐殖质(C2)、类醌化合物(C3)和微生物来源的腐殖质(C4)4种组分。陆源类腐殖质C1可在地下水中富集,占总有机质的40%~55%。相比于地下水,C2和C3则在地表水中占据较高的比例。高砷承压水中C2、C3所占比例高于低砷潜水。其中,C1可以通过络合作用促进溶解性砷浓度的提高,C3作为电子穿梭体可以促进含砷铁氧化物或氢氧化物的还原性溶解从而释放砷。微生物降解有机质生成的HCO-3可以与砷竞争吸附,促进砷的解吸附。此外,还原性溶解产生的Fe(II)与HCO-3形成FeCO3固定一部分的砷。该研究表明,地下水中的天然有机物通过络合作用和作为电子穿梭体促进铁氧化物还原导致地下水砷的富集,为分析黄河上游地区高砷地下水的成因提供理论依据。     

砷的水地球化学及其环境效应

砷在水环境中的迁移和富集可以产生严重的砷污染，砷在自然水系中主要以无机砷酸盐（AsO4^3-）和亚砷酸盐（AsO3^3-）两种形式存在，而砷的有机化合物的含量一般都很低，砷酸盐在富氧化性的水体中占优势，而亚砷酸盐则富集于还原性水体中，水体中As3 和As5 的相对含量主要受氧化还原条件和一些吸附一解吸平衡过程控制，As3 类比As5 类的毒性强得多，而无机砷化合物比有机砷化合物的毒性大，在pH值为5－6时，As^5 不易被还原成气态AsH3，而s^3 却能定量地被还原出来，根据这一性质，可完成水体中As3 和As5 的测定，砷在饮用水中的安全阀值仅为10ug/L，水体中高砷的危害可以通过水质净化予在消除或降低，铁的化学沉淀和吸附法，石灰软化法，活性氧化铝净化法和逆流渗透法等都可以有效地去除或降低饮用水中砷的含量。     

煤燃烧过程中微量元素的迁移和富集

煤中微量元素在燃烧过程中产生迁移与富集。大部分元素在煤的燃烧产物中得以富集,一些挥发性强的元素将扩散到大气中。在飞灰中,大部分环境有害元素的富集程度与其粒度成反比,即在细粒飞灰中更加富集,由此对人体健康的潜在危害也更大。在我国,大型燃煤电厂的环境问题值得重视,同时大量的民用炉灶产生的环境污染更加严重,值得进一步研究与治理。     

煤及其燃烧产物飞灰和底灰中稀土元素地球化学特征及集散规律

采用ICP—MS法测试了褐煤、肥煤和无烟煤以及在不同燃烧条件下获取的飞灰、底灰等29个样品的稀土元素含量;分析了稀土元素地球化学特征。结果表明,不同煤种的稀土元素含量不同,相同煤种在不同燃烧条件下获取的飞灰、底灰中的稀土元素含量也不同;褐煤、肥煤、无烟煤及其燃煤产物飞灰、底灰的稀土元素分布模式呈左高右低的宽缓的“V”型曲线;Eu存在明显负异常。研究了燃煤过程中稀土元素的分布及集散规律,稀土元素在飞灰、底灰中的含量比原煤有明显提高,其增加幅度为几倍至20多倍不等,表明煤炭燃烧后稀土元素在飞灰、底灰中进一步聚集;飞灰和底灰中稀土元素含量、飞灰和底灰对煤的稀土元素含量比和富集因子以及飞灰对底灰的稀土元素含量比和富集因子等,不仅与原煤中稀土元素有直接关系,而且还受锅炉燃烧方式、燃烧温度(炉温)等人为因素的影响。     

石煤中钒元素在燃烧前后赋存状态变化的研究

石煤是一种可综合利用的矿产资源,提取石煤中钒、钼、镍等金属是其综合利用之一.石煤在发电燃烧过程中钒的物相发生显著变化,而钒物相的变化对钒的可浸出性产生较大的影响.笔者采用选择性连续提取方法对四川某地石煤原矿和石煤飞灰进行分析研究,发现石煤原矿中钒主要存在于硅铝酸盐相和有机质相中,部分存在于铁锰氧化物相及吸附态中,极少部分存在于碳酸盐相中.而石煤发电飞灰中钒主要存在于有机质相、硅铝酸盐相和铁锰氧化物相中,少量的钒以吸附态形式赋存.燃烧过程中石煤的各种含钒矿物发生离解,其中的钒得到释放并被氧化成高价态.高价钒一部分与Na、Cl等结合生成可溶性化合物,形成吸附态的钒;另一部分与Fe、Na、Ca等发生反应生成难溶性化合物,并以一定形式富集在飞灰的有机质相、硅铝酸盐相和铁锰氧化物相中.     

地下水砷污染分析

阐述了含砷黄铁矿等含砷矿物以及岩石矿物附着砷等天然来源,同时从气候、环境地质以及水化学环境等方面分析了砷在地下水中的迁移和富集规律。研究表明：干旱、半干旱地区、封闭的地形地貌、断裂凹陷等外部环境有利于高砷地下水的形成,同时含水介质性质、地下水径流条件以及地下水中pH值、Eh值、不同的无机和有机组分对砷在地下水中迁移富集起着重要作用。在此基础上从砷的“来源—影响因素—影响过程—高砷形成”角度提出了地下水砷污染的成因模式,对砷中毒病区的环境问题调查与地下水砷污染的防治具有重要参考价值。     

Arsenic in coal: a review

The review presented covers: (a) historical introduction; (b) some analytical comments; (c) some peculiarities of the As geochemistry in environment; (d) an estimation of coal Clarke value of As; (e) some coals enriched in As; (f) mode of As occurrence in coal; (g) factors influencing the As distribution in coal matter and coal bed; (h) genetic topics; (i) some topics related to environmental impact of As by the coal combustion.The World average As content in coals (coal Clarke of As) for the bituminous coals and lignites are, respectively, 9.0±0.8 and 7.4±1.4 ppm. On an ash basis, these contents are higher: 50±5 and 49±8 ppm, respectively. Therefore, As is a very coalphile element: it has strong affinity to coal matter — organic and (or) inorganic but obligatory authigenic. The coalphile affinity of As is like that for Ge or S.There is strong regional variability of As distribution due to geologic variability of the individual coal basins. For example, bituminous coals in Eastern Germany, Czech Republic and SE China are enriched in As, whereas the coals in South Africa or Australia are very depleted compared to coal Clarke of As. In general, some relationship exists between As content and its mode of occurrence in coals. Typically, at high As content, sulphide sites dominate (pyrite and other more rare sulphides), whereas at low As content, As_org dominates, both being authigenic. A contribution of the terrigenic As (in silicates) is usually minor and of the biogenic As_bio (derived from coal-forming plants) is poorly known.Both organic and inorganic As can exist not only as chemically bound form but also in the sorbed (acid leacheable) arsenate form. With increasing coal rank, sorbed exchangeable arsenate content decreases, with a minimum in the coking coals (German data: the Ruhr coals).Relations of As content in coal to ash yield (or its partitioning in sink–float fractions) and to coal petrographic composition are usually complicated. In most cases, these relations are controlled by main site (form) of As — As_pyr or As_org. If As_pyr dominates, an As accumulation in heavy fractions (or in high-ash coals) is observed, and if As_org dominates, it is enriched in medium-density fractions (or low- and medium-ash coals). Arsenic is in part accumulated in the inertinite vs. vitrinite (As_org ?).There are four genetic types of As accumulation on coal: two epigenetic and two syngenetic: (1) Chinese type—hydrothermal As enrichment, sometimes similar to known Carlin type of As-bearing telethermal gold deposits; (2) Dakota type—hypergene enrichment from ground waters draining As-bearing tufa host rocks; (3) Bulgarian type—As enrichment resulting from As-bearing waters entered coal-forming peat bogs from sulphide deposit aureoles; (4) Turkish type—volcanic input of As in coal-forming peat bog as exhalations, brines and volcanic ash.During coal combustion at power plants, most of the initial As in coal volatilizes into the gaseous phase. At the widely used combustion of pulverized coal, most of As_org, As_pyr and “shielded” As-bearing micromineral phases escape into gaseous and particulate phase and only minor part of As_clay remains in bottom ash. The dominant fraction of escaping As is in fly ash. Because 97–99% of the fly ash is collected by electrostatic precipitators, the atmospheric emission of As (solid phase and gaseous) is usually assumed as rather minor (10–30% from initial As in coal). However, fly ash disposal creates some difficult environmental problems because it is potentially toxic in natural waters and soils. The As leaching rate from ash disposal is greatly controlled by the ash chemistry. In natural environment, As can be readily leached from acid (SiO₂-rich) bituminous coal ashes but can be very difficult from alkali (CaO-rich) lignite ashes.If the As_pyr form dominates, conventional coal cleaning may be an efficient tool for the removing As from coal. However, organic-bound or micromineral arsenic (“shielded” grains of As-bearing sulphides) are not removed by this procedure.Some considerations show that “toxicity threshold” of As content in coal (permissible concentration for industrial utility) may be in the range 100–300 ppm As. However, for different coals (with different proportions of As-forms), and for different combustion procedures, this “threshold” varies.     

煤中铀的赋存分布及其在利用过程中的迁移特征

煤炭与铀两种资源在空间配置和成矿上有关联性,其合理开发利用及污染控制是我国国民经济和社会持续发展的重大需求。基于大量文献调研及前期研究成果,探讨了铀在煤中赋存分布及其在洗选、燃烧、淋滤过程中的迁移特征,取得一些认识:①煤中铀的富集成矿与成煤大地构造演化相关联,西南富铀煤主要与峨眉山玄武岩及断裂构造有关;西北富铀煤一般分布在拗陷和断拗陷盆地开阔地带一侧并与上覆砂岩型铀矿有关。②煤中铀主要与煤中有机质（主要是腐殖酸）结合,富铀煤中铀可以微细粒含铀矿物形式存在,并与有机硫、硫化物紧密共生,故在选煤过程中,无论重选还是浮选,其洗选脱除率均不高（最高为68.3%）,部分煤浮选时铀甚至富集到精煤中;在煤燃烧过程中,铀或多或少都会以气相形式挥发到大气中。③富铀煤一般也同时富集V、Mo、Se、Re、Cr等高价态变价元素,这与有机体深埋分解造成的强还原环境有关,对于那些不变价元素如Sc、Y、La等的沉淀富集主要与腐殖酸形成的酸化条件有关;这些共生组合元素,在富铀煤的分选及煤矸石的淋滤过程中表现出一致的迁移行为。④电厂燃煤过程中铀主要富集（呈数量级的增加）到飞灰和底灰中,粉煤灰中铀淋出浓度一般随淋滤液pH的增加呈降低趋势,其萃取率随灰化温度的升高呈现降低趋势。研究结果为铀资源利用和环境污染控制提供参考和依据。      

贵州普安-晴隆矿区晚二叠世煤及煤灰中伴生元素的富集特征

运用电感耦合等离子体质谱仪（ICP-MS）和电感耦合等离子体发射光谱仪（ICP-AES）分别对普安-晴隆矿区晚二叠世C17、C19、C22和C26号煤层中8个煤样和7个煤灰样进行微量元素含量的测试分析。结果表明,煤及煤灰中明显富集Li、Sc、V、Cr、Co、Ge、As、Nb、Mo、W、U等元素,且各元素在煤灰中更加富集,Nb、Zr、V、Ga和U等伴生金属元素的含量基本达到或超过了对应元素的边界品位或最低工业品位。煤中伴生元素的富集成因研究表明,V、Cr、Co、Nb和Zr等元素的富集主要受物源区峨眉山玄武岩风化碎屑物质供给的控制;U、S、Mo等元素的有限富集与海水作用有关;而受成煤期同沉积火山灰沉降的影响,煤中Li、Nb、Zr、Mo和U等微量元素表现出一致富集的特点;成煤期后的低温热液作用,使得各煤层,尤其是底部煤层（C19、C26）明显富集As、Mo、U和W等元素。综合分析认为,成煤期同沉积的火山灰沉降和成煤期后的低温热液作用是普安-晴隆矿区晚二叠世煤中伴生元素异常富集的主控地质因素。      

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.     

From in-situ coal to fly ash: a study of coal mines and power plants from Indiana

This paper presents data on the properties of coal and fly ash from two coal mines and two power plants that burn single-source coal from two mines in Indiana. One mine is in the low-sulfur (<1%) Danville Coal Member of the Dugger Formation (Pennsylvanian) and the other mines the high-sulfur (>5%) Springfield Coal Member of the Petersburg Formation (Pennsylvanian). Both seams have comparable ash contents (11%). Coals sampled at the mines (both raw and washed fractions) were analyzed for proximate/ultimate/sulfur forms/heating value, major oxides, trace elements and petrographic composition. The properties of fly ash from these coals reflect the properties of the feed coal, as well as local combustion and post-combustion conditions. Sulfur and spinel content, and As, Pb and Zn concentrations of the fly ash are the parameters that most closely reflect the properties of the source coal.     

Sulfur and carbon isotope geochemistry of coal and derived coal-combustion by-products: An example from an Eastern Kentucky mine and power plant

The isotopic compositions of S (δ³⁴S) and C (δ¹³C) were determined for the coal utilized by a power plant and for the fly ash produced as a by-product of the coal combustion in a 220-MW utility boiler. The coal samples analyzed represent different lithologies within a single mine, the coal supplied to the power plant, the pulverized feed coal, and the coal rejected by the pulverizer. The ash was collected at various stages of the ash-collection system in the plant. There is a notable enrichment in ³⁴S from the base to the top of the coal seam in the mine, with much of the variation due to an upwards enrichment in the δ³⁴S values of the pyrite. Variations in δ³⁴S and in the amount of pyritic S in the coal delivered to the plant show that there was a change of source of coal supplied to the plant, between week one and week two of monitoring, supporting a previous study based on metal and sulfide geochemistry for the same plant. The fly ash has a more enriched δ³⁴S than the pulverized coal and, in general, the δ³⁴S is more enriched in fly ashes collected at cooler points in the ash-collection system. This pattern of δ³⁴S suggests an increased isotopic fractionation due to temperature, with the fly ash becoming progressively depleted in ³⁴S and the flue gas S-containing components becoming progressively enriched in ³⁴S with increasing temperatures. Substantially less variation is seen in the C isotopes compared to S isotopes. There is little vertical variation in δ¹³C in the coal bed, with δ¹³C becoming slightly heavier towards the top of the coal seam. An 83–93% loss of solid phase C occurs during coal combustion in the transition from coal to ash owing to loss of CO₂. Despite the significant difference in total C content only a small enrichment of 0.44–0.67‰ in ¹³C in the ash relative to the coal is observed, demonstrating that redistribution of C isotopes in the boiler and convective passes prior to the arrival of the fly ash in the ash-collections system is minor.     

Potential environmental pollution hazards by coal based power plant at Jhansi (UP) India

Coal, a fossil fuel, is the largest source of energy for the generation of electricity in India. In order to study the potential environmental hazards by coal based power plants, particulate matters were collected using Stack Monitoring Kit and gaseous pollutants by Automatic Flue Gas Analyzer. The morphological and chemical properties, mineralogical composition and particle size distributions have been determined by SEM–EDX, XRD and CILAS. The data revealed the presence of particulate matters, SO₂, NOx in the range of 236–315, 162–238, 173–222 mg/Nm³ respectively. The emission of CO₂ was in the range of 43,004–60,115 Nm³/h with an average of 52,830 Nm³/h. Among the elements, Fe > Mn > Al > Zn > B > Ni > Cr > Cu were present in substantially higher proportion than Pb > Mo > Cd > Se > As > Hg. It was found that most of the elements were concentrated on fly ash surface rather than coal, bottom ash and pond ash. This variation may be attributed to the fineness of fly ash particles with large surface ratio to mass. Mineralogical studies of coal and fly ash by X-ray diffraction revealed the presence of mullite, quartz, cristobalite and maghemite. Presence of mullite and quartz found in fly ash indicate the conversion of complex minerals to mullite and quartz at high temperature. Transfer Coefficient was calculated to determine the ratio of the enrichment of trace elements in fly or bottom ash with respect to coal and pond ash.     

粉煤灰土壤主所产蔬菜的有害元素含量变化的环境意义

利用南京第二热电厂湿排的粉煤灰,进行了改良蔬菜土壤的试验,并对试验用的粉煤灰,不同施灰量的土壤及所产蔬菜的３８个样品的有害元素和放射性元素含量进行了系统的测定。结果表明：这些元素在土壤中的含量与粉煤灰施用量无明显相关性;在本次试验范围内施用粉煤灰没有造成土壤的污染,其所产蔬菜的这些元素含量也均低于国家卫生标准限值,食用是安全的。     

Geochemistry, mineralogy, and technological properties of the main Stephanian (Carboniferous) coal seams from the Puertollano Basin, Spain

This study is focused on the occurrence and distribution of mineral matter and major and trace elements in the high volatile bituminous coal from Puertollano (south-central Spain). The relationship between ash behaviour and inorganic composition, as well as the possible formation of fouling and slagging deposits in boilers during the conversion process, were investigated. The Puertollano coals do not exhibit plastic properties, despite their rank, probably because of their high ash and inertinite contents.The Puertollano coal has medium to low total S content (0.48% to 1.63% db, with a mean of 1.0% db) and is characterised by relatively high contents of Si, Pb, Sb, and Cs. Some elements such as As, Cd, Co, Cr, Cu, Ge, Li, Mn, Ni, W, and Zn are also present in relatively high contents. The enrichment in a number of heavy metals could be attributed to the common sulphide ores occurring near the Puertollano coal deposit.The following trace elements affinities are deduced: (a) sulphide affinity: As, Co, Cd, Cu, Ni, Sb, Tl, and Zn; (b) aluminum–silicate affinity: K, Ti, B, Co, Cr, Cs, Cu Ga, Hf, Li, Nb, Rb, Sn, Ta, Th, V, Zr, and LREE; (c) Carbonate affinity: Ca, Mg, Mn, and B; (d) organic affinity: B.The very high Si levels and the anomalous enrichment in Cs, Ge, Pb, Sb, and Zn shown by the Puertollano coals account for the high contents of these elements in the Puertollano fly ash when compared with the other Spanish coal fly ashes.The chemical composition of the high temperature ash (HTA) is consistent with the trend shown by the ash fusion temperatures (AFT) and also with the predictive indices related to slagging and fouling propensities. Thus, the ash fusion temperatures increase with high values of Al₂O₃ as well as with the decrease in Fe₂O₃, CaO, and MgO.     

粉煤灰土壤及所产蔬菜的有害元素含量变化和环境意义

利用南京第二热电厂湿排的粉煤灰,进行了改良蔬菜土壤的试验,并对试验用的粉煤灰、不同施灰量的土壤及所产蔬菜共３８ 个样品的有害元素和放射性元素含量进行了系统的测定。结果表明：这些元素在土壤中的含量与粉煤灰施用量无明显相关性;在本次试验范围内施用粉煤灰没有造成土壤的污染;其所产蔬菜的这些元素含量也均低于国家卫生标准限值,食用是安全的。