岩溶区典型石灰土Cd形态指示意义及风险评价——以桂林毛村为例

为了了解岩溶区石灰土中重金属Cd形态分配特征及富集情况,在桂林毛村采集了3种处于不同发育阶段的黑色、棕色和红色石灰土进行研究。通过原子光谱仪测试了Cd质量分数,运用改进的Tessier分析法测定了3种石灰土中Cd的可交换态(EXC)、碳酸盐结合态(CAB)、铁锰氧化物结合态(OXI)、有机结合态(ORG)、残渣态(RES)5种形态,并对其指示意义及风险进行了分析与评价,结果表明,3种石灰土中Cd质量分数从大到小依次为早期黑色石灰土、中期棕色石灰土、晚期红色石灰土。形态测试结果表明:黑色石灰土和棕色石灰土中Cd形态以铁锰氧化态和残渣态为主,占土壤Cd质量分数的63%以上,且5种形态质量分数从大到小顺序均为铁锰氧化态、残渣态、可交换态、碳酸盐结合态、有机结合态;红色石灰土Cd形态以残渣态为主,占土壤Cd质量分数的76%,形态分配特征从大到小为残渣态、铁锰氧化态、可交换态、碳酸盐结合态、有机结合态。Cd稳定度和富集程度评价结果表明:在黑色石灰土、棕色石灰土和红色石灰土中Cd稳定度逐渐减小,环境二次释放风险逐渐降低;富集程度从大到小依次为黑色石灰土、棕色石灰土、红色石灰土,其中Cd在黑色石灰土中呈显著富集状态,在棕色石灰土中呈中度富集状态,在红色石灰土中呈轻微富集状态。潜在生态风险评价和健康风险评价结果表明,由早期黑色石灰土到中期棕色石灰土和晚期红色石灰土,土壤中Cd的生态风险和健康风险均逐渐降低。研究结果可为岩溶区土壤重金属Cd污染修复与治理提供基础数据。     

北京城区土壤中Hg、Pb、Cd、Cu及Zn化学形态及环境效应

为弄清北京城区土壤中Hg、Pb、Cd、Cu及Zn五种重金属元素的化学形态分布特征,系统采集了126件城区表层土壤样品,采用连续提取法对重金属元素各化学形态含量进行了测定。结果表明:土壤中土壤中Hg、Pb、Cd、Cu、Zn含量差异显著。Hg元素以残渣态和强有机结合态为主,Cd元素离子交换态、碳酸盐结合态、残渣态、铁锰氧化物结合态含量较高,Pb、Cu、Zn元素以残渣态、铁锰氧化物结合态为主。Hg元素的有效态含量最低(不足1%),现情况下不会对环境造成污染;Cd元素的有效态含量最高(40%),生物有效性和潜在生态危害性较大,运用植物修复技术对其治理为经济有效的方法;Pb、Cu、Zn有效态含量较低(约10%),生物有效性和潜在生态危害性均有限。各元素形态与全量之间相关程度虽有差别,但基本呈正相关关系。     

类芽孢杆菌对铜陵新桥矿区土壤中Cu化学形态的影响

采用Tessier五步连续提取法和红外光谱技术,研究类芽孢杆菌对铜陵新桥矿区重金属污染土壤中Cu化学形态的影响,初步探讨了Cu形态变化的机理。结果表明,不同投入量的类芽孢杆菌接种到土壤培养一周后,土壤溶液pH值降低,土壤中可交换态、有机结合态Cu含量增加,碳酸盐结合态、铁锰氧化物结合态和残渣态Cu的含量降低。土壤中可交换态、铁锰氧化物结合态和残渣态Cu含量的变化主要受土壤溶液的pH值控制;有机结合态升高主要与类芽孢杆菌菌数及其代谢产生的低分子量有机酸有关。类芽孢杆菌可以改变矿区土壤中Cu的化学形态,影响Cu的生物有效性。     

茶园土壤不同形态镍的含量及其影响因素

通过自然茶园土壤采样和室内实验分析,探讨浙江、江苏和安徽13个茶园土壤镍的污染状况、形态分布规律以及不同形态镍的含量与土壤镍总量和土壤理化性质的关系。结果表明：部分茶园土壤受到不同程度的镍污染;茶园土壤镍的形态分布有一定差异,按镍的含量多少排序,一般为残渣态＞交换态＞铁锰氧化物结合态＞有机结合态＞碳酸盐结合态;除了交换态以外的所有其他形态的镍含量均随土壤镍含量的增加而显著增加;碳酸盐结合态、铁锰氧化物结合态和残渣态镍含量随土壤pH的升高呈显著增加趋势,而交换态镍则呈减少趋势,但不显著;随土壤有机质含量的增加,铁锰氧化物结合态镍显著减少,而其他形态增加或减少的趋势均不显著;碳酸盐结合态、有机结合态和残渣态的镍含量均随阳离子交换量的增加显著增加;随粘粒含量的增加所有形态中的镍呈增加趋势,但除了残渣态外增加趋势均不显著。     

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。     

再生铅工业园周边土壤重金属分布特征及来源解析

通过对安徽再生铅工业园周边0～20 cm深度的表层土壤及0～300 cm深度的剖面土壤中重金属含量、分布特征、赋存形态的研究及来源解析,发现土壤中Cd、Hg、As、Pb、Cr、Cu、Ni及Zn含量平均值分别为300.4 ng/g、39.45 ng/g、12.22 mg/kg、42.5 mg/kg、75.4 mg/kg、28.5 mg/kg、33.5 mg/kg、74.1 mg/kg,富集元素主要有Cd、Pb及Hg,其中土壤Cd、Pb富集明显受工业活动影响,Hg富集与工业活动无关。土壤Cd明显富集面积为21 km~2,影响深度为65 cm。土壤Pb明显富集面积为12 km~2,影响深度为20 cm。土壤Hg普遍为中度富集,富集深度为0～65 cm。土壤中Cd以碳酸盐结合态为主,其次为铁锰氧化物结合态,Pb以残渣态、铁锰氧化物结合态为主。Cd的碳酸盐结合态和铁锰氧化物结合态、Pb的残渣态和铁锰氧化物结合态均与其全量呈显著正相关。研究区土壤环境质量较好,仅有9.5%样点Cd含量与5.4%样点Pb含量超过了《GB 15618—2018土壤环境质量农用地土壤污染风险管控标准(试行)》规定的污染风险筛选值。     

城乡交错区土壤中镉的赋存形态及其生物有效性研究

采用连续形态分析方法研究了重庆市城乡交错区土壤中Cd的形态分布及其与莴笋吸收Cd量的关系.结果表明,研究区土壤和莴笋中Cd污染严重,土壤各形态Cd总体分布特征为:残渣态Cd＞有机质结合态Cd＞离子交换态Cd＞碳酸盐结合态Cd＞铁锰氧化物结合态Cd＞水溶态Cd,其中活性较强的交换态Cd(包括水溶态Cd和离子交换态Cd)比重较大.Cd在土壤中的分布与土壤中的物理性粘粒及粉粒含量密切相关.而在土壤各形态Cd中,离子交换态Cd具有较高的生物有效性.研究区土壤和蔬菜中Cd污染已经较严重,建议加强城乡交错区的环境综合管理.     

土壤pH对镉存在形态影响的模拟实验研究

通过模拟实验,研究了土壤pH对水稻土、紫色土和黄壤的水溶态、可交换态、碳酸盐态、铁锰氧化态、有机结合态和残渣态Cd含量的影响。结果表明:在中碱性条件下,水溶态Cd质量分数比值小于3%,但pH<6.5时,水溶态Cd含量随着pH 减小迅速增加, pH 为4. 57 时,水稻土水溶态Cd 质量分数比值最高达48 39%;可交换态Cd含量在碱性条件下,随着土壤pH值增大迅速下降,在酸性区域内,可交换态Cd含量随pH增加呈上升趋势;碳酸盐态和铁锰氧化态Cd含量随土壤pH增大而增加;有机结合态Cd含量随土壤pH增加而增大,但变化幅度不大。对Cd污染的土壤进行治理时,控制土壤pH大于6.5以及增施有机肥等是减少Cd对生态系统危害的关键。     

干旱区绿洲土壤共存重金属元素形态变化及生物有效性实验分析——以Cd、Zn、Ni元素为例

采用盆栽试验,初步研究了干旱区绿洲土壤—胡萝卜系统中镉、锌、镍3种重金属的形态变化特征及其生物有效性问题。结果表明:供试绿洲土壤原状土中,Cd、Zn、Ni均以稳定的残渣态形式存在,而处理土壤中重金属被钝化的量有限,Cd的存在形式主要以碳酸盐态为主,Zn、Ni则主要以铁锰氧化态为主;3种元素的活性大小依次为Cd>Ni>Zn。根据回归分析,元素Zn对胡萝卜块茎和茎叶吸收Zn量贡献最大的分别是Zn的碳酸盐结合态和铁锰氧化态;元素Ni对胡萝卜各部位吸收贡献最大的均为Ni的铁锰氧化态。     

干旱区绿洲土壤共存重金属元素形态变化及生物有效性实验分析

采用盆栽试验,初步研究了干旱区绿洲土壤—胡萝卜系统中镉、锌、镍3种重金属的形态变化特征及其生物有效性问题。结果表明：供试绿洲土壤原状土中,Cd、Zn、Ni均以稳定的残渣态形式存在,而处理土壤中重金属被钝化的量有限,Cd的存在形式主要以碳酸盐态为主,Zn、Ni则主要以铁锰氧化态为主;3种元素的活性大小依次为Cd＞Ni＞Zn。根据回归分析,元素Zn对胡萝卜块茎和茎叶吸收Zn量贡献最大的分别是Zn的碳酸盐结合态和铁锰氧化态;元素Ni对胡萝卜各部位吸收贡献最大的均为Ni的铁锰氧化态。     

岩溶地区现代土壤与洞穴石笋中单甲基支链烷烃与烷基环己烷对比研究

利用GC-MS（气相色谱—质谱仪）,对采自湖北清江流域和尚洞洞顶的土壤样品与洞内石笋样品进行分析,发现土壤中存在的七个系列单甲基支链烷烃在所有的石笋样品中均可以找到,呈现相似的分布模式,石笋中七个系列支链烷烃有可能来自洞穴滴水携带的土壤中的支链烷烃,但是也不能排除石笋原地生长的微生物的贡献。烷基环己烷的分布在土壤与石笋中呈现了相似的分布模式,但是主峰碳数有所变化,高碳数部分与低碳数部分的相对含量也发生了变化。主要原因可能是微生物选择性降解的结果,也有可能是土壤与石笋中微生物种类分布差异所造成的。本次研究初步显示了相对封闭稳定的洞穴沉积物与上覆土壤层中生物标志化合物的异同。      

Hydrogen and carbon in solid solution in oxides and silicates

The dissolution of H₂O and CO₂ in structurally dense, nominally anhydrous and non-carbonate oxide matrices such as MgO and CaO is reviewed. H₂O and CO₂ are treated as gaseous oxide components which enter into solid solution with the refractory oxide hosts. They form anion complexes associated with cation vacancy sites. Evidence is presented that OH^? pairs which derive from the dissolution of H₂O are subject to a charge transfer (CT) conversion into peroxy moieties and molecular hydrogen, O ₂ ^2? ... H₂. Because the O ₂ ^2? moiety is small (O^?-O^? distance ≈ 1.5 Å) high pressure probably favors the CT conversion. Mass spectroscopic studies show that molecular H₂ may be lost from the solid which retains excess oxygen in the form of O ₂ ^2? , leading to the release of atomic O. The dissociation of O ₂ ^2? moieties into a vacancy-bound O^? state and an unbound O^? state can be followed by measuring the internal redox reactions involving transition metal impurities, the transient paramagnetism of the O^? and their effect on the d.c. conductivity. Evidence is presented that CO₂ molecules dissolve dissociatively in the structurally dense oxide matrix, as if they were first to dissociate into CO+O and then to form separate solute moieties CO ₂ ^2? and O ₂ ^2? , both associated with cation vacancy sites. In the CO ₂ ^2? moiety (C-O^? distance 1.2–1.3 Å, OCO angle ≈ 130°) the C atom probably sits off center. The transition of the C atom into interstitial sites is accompanied by dissociation of the CO ₂ ^2? moiety into CO^? and O^?. This transition can be followed by infrared spectroscopy, using OH^? as local probes. Further support derives from magnetic susceptibility, thermal expansion, low frequency dielectric loss and low temperature deformation measurements. The recently observed emission of O and Mg atoms besides a variety of molecules such as CO, CO₂, CH₄, HCN and other hydrocarbons during impact fracture of MgO single crystals is presented and discussed in the light of the other experimental data.     

Geogenic and anthropogenic zinc in epiphytic and terricolous lichens in Finland

At 31 sites in Finland the Zn content was determined of the epiphytic lichen Hypogymnia physodes (L.) Nyl. growing on pine and birch, the terricolous lichen Cladina spp. in pine bark, and the inner part of birch bark. The anomalous contents of Zn in H. physodes on pine and Cladina spp. in soil appeared to be strongly related to sulphide ore deposits. Anthropogenic Zn correlated closely with S and Fe in H. physodes on pine and with Fe in Cladina spp. The binding of geogenic Zn was related to iron hydroxides, and was attributed to the different uptake mechanism of S in these lichens. Elevated values of Zn in H. physodes on birch were due to both geogenic and anthropogenic sources. Zinc in pine bark increased with the Zn content in H. physodes and reached a limiting value.     

Comparative urbanization in Ghana and Kenya in time and space

There are few inter-African country urban analyses because of the continent’s enormous size and socioeconomic diversity, language barriers, and wide variations in national and regional urban research capacity. Nevertheless, comparative urban studies are critical in understanding contemporary African urbanization. In this comparative spatial and temporal analysis of Ghana and Kenya’s urbanization, we find that both countries are urbanizing rapidly and are faced with many common urban problems. Moreover, Ghana is more urbanized than Kenya and has a larger indigenous urban imprint and a more widely dispersed urban pattern. Besides their physiographic and population conditions, we trace these countries’ convergent and divergent urban trends to their shared but unique experiences of colonialism, nationalism and globalization.     

Temporal and spatial variations in water discharge and sediment load in the Alaknanda and Bhagirathi Rivers in Himalaya, India

The Alaknanda and Bhagirathi Rivers originate in the mountainous regions of the Himalayas (Garhwal) and result in high sediment yields causing flood hazards downstream of the Ganga River and high sediment flux to the Bay of Bengal. The rivers are perennial, since runoff in these rivers is controlled by both precipitation and glacial melt. In the present study, three locations in the upper reaches of the Ganga River were monitored for 1 yr (daily observations of, more than >1000 samples) for suspended sediment concentrations. In addition, more than one hundred samples were collected from various locations of the Alaknanda and Bhagirathi Rivers at different periods to observe spatial and temporal variations in river suspensions. Further, multi-annual data (up to 40 yrs) of water flow and sediment concentrations were used for inferring the variations in water flow and sediment loads on longer time scales. In most previous studies of Himalayan Rivers, there has been a general lack of long term water flow and sediment load data. In the present study, we carried out high frequency sampling, considered long term discharge data and based on these information, discussed the temporal and spatial variations in water discharge and sediment loads in the rivers in the Himalayan region. The results show that, >75% of annual sediment loads are transported during the monsoon season (June through September). The annual physical weathering rates in the Alaknanda and Bhagirathi River basins at Devprayag are estimated to be 863 tons km⁻² yr⁻¹ (3.25 mm yr⁻¹) and 907 tons km⁻² yr⁻¹ (3.42 mm yr⁻¹) respectively, which are far in excess of the global average of 156 tons km⁻² yr⁻¹ (0.58 mm yr⁻¹).     

Discovery of Cinnabar in Soils in Hg Anomalous Zones in City and Town Areas and Their Surroundings and Its Significance

As a result of systematic study on heavy minerals in soils at city and town areas and their surroundings,cinnabar was discovered for the first time in areas of Hg anomalies in China, and it was found that the distribution of cinnabar was basically coincident in scope with that of Hg anomalies, showing that Hg anomalies were‘closely related to cinnabar. This finding provides a theoretical basis for a verification of Hg anomalies in soils in city and town areas and their surroundings, as well as evaluation of its ecological effects, and is significant to revealing the occurrence modes and origin of Hg in soils.     

煤中气孔和镶嵌结构及其在煤变质研究中的意义

河南省禹县、新密和荥巩煤田山西组Ⅱ₁煤的贫煤和无烟煤中,气孔发育。气孔形态有椭圆状（图版1）、圆状及不规则状（图版2）,有的几个气孔连在一起呈大的朵状气孔(图版3)。此外,在荥巩煤田西部无烟煤中还发育有镀嵌结构(图版4)。      

Trends in Analytical Developments and Earth Science Applications in LA-ICP-MS and LA-MC-ICP-MS for 2004 and 2005

This review of laser ablation-inductively coupled plasma-mass spectrometry includes research that employed quadrupole instruments, and single-collector and multicollector magnetic sector field instruments. The most important trend in 2004–2005 was the growing appreciation that small matrix effects in LA-(MC)-ICP-MS need to be addressed in order to produce highly precise and accurate data by the method. The issue is most acute for isotope ratio measurements that require standard-sample-standard bracketing but can also be important for certain elemental analysis. Matrix-dependent elemental and isotopic fractionations were studied from the standpoint of laser-sample interactions and the behaviour of laser-generated particles in the ablation cell, transfer tubing and ICP torch. Innovations in LA-(MC)-ICP-MS involved signal smoothing, in torch laser ablation, on-line isotope dilution and molecular oxide monitoring. Other important research was carried out on the calibration and homogeneity of various reference materials; and the exploration of mature ( in situ U-Pb geochronology) and emerging (apatite fission-track chronometry, U-Th/He thermochronology, boron/strontium/uranium-series isotopic microanalysis) applications in the Earth sciences.     

Regional gravity survey and application in oil and gas exploration in China

Ground gravity survey for regional structure unit delineation and oil and gas exploration in China is addressed in this paper with examples. Gravity survey scales, coverage, technical regulations and achievements at the national level are introduced, including data processing and anomaly interpretation techniques. Bouguer anomalies of terrestrial territories of China and classification of anomalous feature zones are also described; they are well correlated with lithotectonical boundaries, fault zones, and unexposed igneous plutons. Recent study results of petroliferous sedimentary basins are presented as well, including concealed boundaries and major structures of large basins. It is concluded that gravity survey is the most effective and economic method in unveiling unexposed and deep-seated structures, targeting and delineating oil and gas-bearing sedimentary basins, and locating main trap structures within prolific basins in early stage of exploration in China. Suggestions for improving exploration of both conventional and unconventional oil and gas reservoirs in China are also given in the paper.     

Re-Os and Pd-Ag systematics in Group IIIAB irons and in pallasites

Using improved analytical techniques, which reduce the Re blanks by factors of 8 to 10, we report new Re-Os data on low Re and low PGE pallasites (PAL-anom) and IIIAB irons. The new pallasite samples nearly double the observed range in Re/Os for pallasites and allow the determination of an isochron of slope 0.0775 ± 0.0008 (T = 4.50 ± 0.04 Ga, using the adjusted λ¹⁸⁷Re = 1.66 × 10⁻¹¹ a⁻¹) and initial (¹⁸⁷Os/¹⁸⁸Os)₀ = 0.09599 ± 0.00046. If the data on different groups of pallasites (including the “anomalous” pallasites) are considered to define a whole-rock isochron, their formation would appear to be distinctly younger than for the iron meteorites by ∼60 Ma. Five IIIAB irons (Acuna, Bella Roca, Chupaderos, Grant, and Bear Creek), with Re contents ranging from 0.9 to 2.8 ppb, show limited Re/Os fractionation and plot within errors on the IIAB iron meteorite isochron of slope 0.07848 ± 0.00018 (T = 4.56 ± 0.01 Ga) and initial (¹⁸⁷Os/¹⁸⁸Os)₀ = 0.09563 ± 0.00011. Many of the meteorites were analyzed also for Pd-Ag and show ¹⁰⁷Ag enrichments correlated with Pd/Ag, requiring early formation and fractionation of the FeNi metal, in a narrow time interval, after injection of live ¹⁰⁷Pd (t_1/2 = 6.5 Ma) into the solar nebula. Based on Pd-Ag, the typical range in relative ages of these meteorites is ≤10 Ma. The Pd-Ag results suggest early formation and preservation of the ¹⁰⁷Pd-¹⁰⁷Ag systematics, both for IIIAB irons and for pallasites, while the younger Re-Os apparent age for pallasites suggests that the Re-Os system in pallasites was subject to re-equilibration. The low Re and low PGE pallasites show significant Re/Os fractionation (higher Re/Os) as the Re and PGE contents decrease. By contrast, the IIIAB irons show a restricted range in Re/Os, even for samples with extremely low Re and PGE contents. There is a good correlation of Re and Ir contents. The correlation of Re and Os contents for IIIAB irons shows a similar complex pattern as observed for IIAB irons (Morgan et al., 1995), and neither can be ascribed to a continuous fractional crystallization process with uniform solid-metal/liquid-metal distribution coefficients.