Considerations regarding the definition of a geochemical baseline of elements in the surficial materials in areas differing in basic geology

The problem of a geochemical baseline in areas differing in basic geology was studied by comparing the results of regional geochemical mapping programmes undertaken in Finland and Lithuania using different sample media and a variety of analytical methods. The authors discuss issues relevant to the definition of a geochemical baseline.Most of the differences in geochemical baselines between Lithuania and Finland are due to the dissimilarities in basic geology, which in Lithuania is controlled by Palaeozoic and Mesozoic sedimentary rocks, but in Finland by Archaean and Proterozoic metamorphic and intrusive rocks. Other important factors are the geological processes that after the last glaciation created the present surficial materials. In Finland, for instance, the abundances of potentially harmful elements derived from crystalline bedrock tend to be higher than in Lithuania. However, in both countries element concentrations are higher in finely-grained marine and lacustrine sediments than in glacial till, and they are also higher in the finer grain size fractions than in the coarser fractions of till samples. Only a small proportion of the total heavy metal concentrations is bioavailable. Thus the baseline concentrations depend not only on the basic geology, but also on sample material collected, its grain size and the extraction method.     

Estimation of weathering rates for critical load calculations in Finland

 The formation of base cations through mineral weathering in forest soils is one of the key parameters in calculating critical loads. Weathering rates in Finland have been estimated using a variety of methods. In the first approach, three weathering rate categories were assigned to soils according to the bedrock type. The second approach was based on an empirical relationship obtained from Swedish field studies. Changes in zirconium content through the soil profile were used to estimate element losses in soil after deglaciation. These calculated losses correlated well with the total calcium and magnesium concentrations in till C-horizons and the effective temperature sum (ETS). Comprehensive geochemical data for the parent till fine fraction (<0.06 mm) was available through the reconnaissance scale till geochemical mapping program of the Geological Survey of Finland (GSF). The equations obtained from Swedish studies were based on the use of the coarse (<2.0 mm) till fraction, and the differences in element concentrations between the fine and coarse size fractions remained a potential source of uncertainty estimating overall weathering rates. In the third approach, new geochemical data from the <2.0 mm till fraction from southern Finland were used to make new weathering rate estimates. The use of soil geochemistry instead of bedrock map classification clearly led to an improvement in the estimates of soil weathering rates in glacied terrains. The use of the fine till fraction (<0.06 mm) in the zirconium approach generally resulted in overestimations of the weathering rate. The new geochemical data for the coarse till fraction (<2 mm) are now consistent with the input requirements of the zirconium method, although the results still require further evaluation. Finnish soil profiles have a shorter weathering history than most of the Swedish ones and the uppermost layer in Finnish podsols has in some cases developed in a different till layer than the C-horizon. Received: 15 October 1995 · Accepted: 8 March 1996     

Geochemical Atlas of Finland: preliminary aspects

During 1984 and 1985, the Geological Survey of Finland carried out regional geochemical mapping of till, at a scale of 1:2,000,000, as part of a programme to produce data for the first Geochemical Atlas of Finland. The Atlas is designed to give comprehensive background information on the distribution of elements in rocks, soils, and the surficial environment.     

Till geochemistry in the ribbed moraine area of Peräpohjola,Finland

The characteristics of ribbed moraines, with an emphasis on till geochemical prospecting, were studied in the area of Peräpohjola, southern Finnish Lapland. Percussion drilling, test pits and trenches were used for till sampling. The samples were partially extracted and then analysed using ICP-AES or GFAAS methods in the geolaboratory of the Geological Survey of Finland. The distribution of Au and Cu in fine fraction (<0.06 mm) of till in both horizontal and vertical dimensions showed that the uppermost part of the moraine ridges contained the highest metal contents. In the coarser fractions of till (0.06–0.5 and >2 mm), the anomalies were located on the distal side of the ribbed moraine ridges, down-ice from mineralized bedrock. Geochemical patterns together with fresh pyrite grains in till heavy mineral concentrates indicate a short glacial transport distance of the mineralized debris. This conclusion is also supported by the presence of a large proportion of local rock fragments and boulders in the uppermost till unit and at the surface, which is a result of glacial quarrying during the ribbed moraine formation.     

Gold contamination of the fine fraction of till during sampling and sample preparation

Contamination of gold ring and natural gold grains into plastic capsules used in INAA analysis and the fine fraction of till (0.064 mm) have been studied. An artificial contamination of till samples with a gold ring caused Au contents of 100–600 ppb in the fine fraction. A few rubbings of plastic capsules with a gold ring gave Au amounts of 15–170 ng per capsule. Natural gold grains of sizes 0.1–1.0 mm added into “gold-free” till samples before drying and sieving caused Au contents of 1–27 ppb into the fine fraction. In a regional geochemical survey an anomaly of a few hundreds of square kilometers with concentrations of 100–600 ppb Au in the fine fraction of till was observed. Later studies showed that this area was very low in Au, concentrations being generally below one ppb. The anomaly was interpreted as a contamination caused by the gold rings of the samplers.     

Geochemical mapping and databases in Finland

Regional geochemical maps in Finland have been produced from many different programmes. The scale of sampling, the material collected and the analytical methods used varied according to the aim of the study. The entire country was covered at a reconnaissance scale using glacial till, groundwater, surface water and organic stream sediments as sampling media. Glacial till was sampled throughout the country at a regional scale. Local scale mapping and detailed geochemical studies are carried out in selected areas. The main analytical methods have been ICP-AES and ICP-MS, but other methods were used when necessary. In assaying solid material, both total decomposition and strong acid (aqua regia) leaching were used. The results are stored in ALKEMIA, a database developed in the geochemistry department of the Geological Survey of Finland. The data are available as tabulated ASCII files and as digital image files on diskettes, or as various types of symbol and colour maps from desired areas or map sheets. Two examples of the application of geochemical mapping data in prospecting and in environmental research are presented. Indications of the presence of gold and multiple-sulphide ore deposits have been the most useful results obtained from a prospecting standpoint. On the environmental side, reconnaissance scale geochemical mapping data gave more reliable information on the base cation concentration than bedrock maps, making them particularly valuable in devising an acidification assessment model.     

Geochemical Baselines of Nickel and Chromium in Various Surficial Materials in the Barents Region, NW Russia and Finland

The geochemical baselines of nickel and chromium were studied from the data produced by the Barents Ecogeochemistry project, a large international regional geochemical mapping exercise. The project surveyed major and trace element distributions in stream water, organic and mineralogically-modified soil horizons, and terrestrial moss in the northwestern part of Russia and in Finland. Other materials were collected during the pilot phase and later from thirty special sites. The results on respective materials by XRF, ICP-MS and ICP-AES showed that both geological and anthropogenic factors have an influence on the geochemical baseline concentrations of Ni and Cr in organic soil and stream water. The main explanation of the observed distribution patterns in terrestrial moss is human activity, but geological factors can also affect the baselines. The variation of geochemical baselines in the mineral-rich soil horizon depends only on variations in bedrock. The mineralogy of samples mainly controls the leachability properties of soil samples.     

安徽省江淮流域土壤地球化学基准值与背景值研究

基于安徽省江淮流域多目标区域地球化学调查数据资料,统计获得了表层和深层土壤地球化学基准值、背景值及相应的地球化学参数,为研究区生态环境评价及相关学科研究提供了基础。研究表明,成土母质类型对土壤元素地球化学基准值影响显著,表层土壤化学组成表现出既对深层土壤具有一定的继承性,又在表生作用下发生某些变化:表层土壤中迁移活动性强的元素和人为扰动污染的元素明显不同于深层土壤;随着地理空间位置的变化,同类成土母质形成环境、成因来源的差异导致其化学组成的空间变异,造成不同地区同类成土母质地球化学基准值有所不同。因此,土壤地球化学基准值研究应更多地考虑地质背景、物质来源等因素的影响。     

Influence of parent sediments on the concentration of heavy metals in urban and suburban soils in Turku,Finland

The purpose of this study was to examine the influence of parent sediment material on soil geochemistry and to locate possible pollution sources in the area of Turku town in southwestern Finland. The study area is glaciated terrain and subsurface samples were chosen to represent five different parent sediment materials: glacial till, glaciofluvial or littoral sand, clay, peat and marine mud. Elemental concentrations of surface (100 samples) and background soil (50 samples) were analysed by ICP-AES (Al, Ba, Ca, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, S, Sr, Ti, V) and by graphite furnace AAS (As, Cd, Mo, Se). Loss-on-ignition was determined as an indicator of organic matter. Analytical results were examined using multivariate statistical methods. The results indicate that the studied soils are not heavily contaminated; there were only few sample sites with elevated heavy metal concentrations. High Pb concentrations were observed along main traffic routes, and also in places where there has been small-scale use of antifouling paints. However, concentrations of heavy metals in topsoil were in general significantly lower than those measured in large cities elsewhere. The parent material strongly affects the geochemical character of the soils. Clays naturally have a significantly higher concentration of heavy metals than sands or till material. This is also reflected in concentrations in organic topsoil. When assessing target levels for polluted soil, the primary sediment appears to be a more important factor than the amount of organic matter.     

Heavy metal contamination in overbank sediments of the Geul river (East Belgium): Its relation to former Pb-Zn mining activities

Overbank sediments of the Geul River (East Belgium) are highly contaminated by the heavy metals Pb, Zn, and Cd due to former Pb-Zn mining activities in the drainage basin. Geochemical variations in vertical overbank sediment profiles sampled 1 km north of the mine tailings of Plombiéres allow metal fluxes back to the 17th century to be reconstructed. The vertical profiles are subdivided into three major units corresponding to different industrial periods based on sedimentological criteria as well as on the distribution of contaminants. Alluvial sediments with the highest heavy metal concentrations correspond to the major period of mining activity of the 19th century. The fact that Zn mining at the La Calamine open mine started before large-scale mining of the PbS-ZnS subsurface exploitations is reflected in the vertical profiles by an increase in Zn content before a marked increase in Pb and Cu. The regional extent of contamination in the alluvial deposits was evaluated on the basis of the geochemical analysis of sediments at depths of the 0–20 cm and 80–100 cm. Most of the upper samples are extremely contaminated. Significant local variations in heavy metal concentration in the lower samples are interpreted in terms of which overbank sediment horizon has been sampled at a depth of 80–100 cm. This indicates that blind sampling of overbank sediments to characterize the degree of contamination in shallow boreholes can give very erratic results.     

Glacial dispersal studies using indicator minerals and till geochemistry around two eastern Finland kimberlites

Diamondiferous kimberlites occur in eastern Finland, in the areas of Kaavi–Kuopio and Kuhmo. Active diamond exploration has been ongoing in the country for over two decades, but the Karelian craton still remains under explored given its size and potential. In order to develop techniques that can be applied to diamond exploration in glaciated terrains, the Geological Survey of Finland (GTK) carried out a detailed heavy mineral and geochemical survey of Quaternary till in 2001–2003 around two of the known kimberlitic bodies in Finland, Pipe 7 in Kaavi and Dyke 16 in Kuhmo. The mineralogical and geochemical signatures of these two kimberlites were studied in the basal till deposited down-ice from the targets. The kimberlites were selected to represent two different types in terms of shape, size, age and petrology, as well as showing contrasting country rocks and Quaternary deposits. Till samples up to 60 kg in weight were taken by excavator and by drill rig. Kimberlitic indicator mineral grains (0.25–1.0 mm) were concentrated using a GTK modified 3″Knelson Concentrator. Fine fractions (< 0.063 mm) of selected samples were analyzed by XRF and ICP-MS. The indicator grains down-ice from Pipe 7 form a well-defined fan in the basal till that can be followed for at least 2 km with a maximum concentration at 1.2 km distance from the pipe. Another kimberlitic body discovered during the study 300 m down-ice from Pipe 7 demonstrates that there are in fact at least two superimposed indicator fans. The results do not rule out the possibility of even more undiscovered kimberlitic sources in the area. In contrast, the indicator dispersal trail from Dyke 16 is shorter (1 km) and less well-defined than that at Kaavi, mainly due to the lower indicator content in the kimberlite itself and subsequently in till, as well as a large population of background chromites in till. The latter population is likely having been derived from the Archean Näätäniemi serpentinite massif and the associated ultramafic metavolcanics of the Kuhmo greenstone belt, located ca. 30 km up-ice from the sampling area. The indicator maximum at Seitaperä dyke swarm occurs immediately down-ice from the kimberlite, after which the concentration drops rapidly. Results of this study contribute to the overall understanding of the Quaternary history of the Kaavi and Kuhmo areas, and more importantly, provide key information to diamond exploration in these particular regions and also elsewhere in glaciated terrains.     

现代地质工作重要发展领域:“十一五”期间勘查地球化学评述

"十一五"期间(2006—2010年),国土资源部中国地质调查局继续推进区域化探与多目标区域地球化学调查计划。在区域化探方面,完成调查面积82.93万km2(累计完成756.62万km2),发现异常4 708处,经验证发现各类矿产411处,其中有色金属矿产273处,占66.4%,取得重大找矿突破。开展矿产资源地球化学评价,通过建立典型矿床地球化学异常模式,来圈定找矿靶区和进行资源潜力定量预测。在多目标区域地球化学调查方面,完成调查面积26.56万km2(累积完成165.66万km2),建立生态地球化学评价体系,主要针对重金属元素成因来源、迁移转化、生态效应与变化趋势进行较为全面和深入的研究。土地质量地球化学评价表明,中国土地达到优质级占53%,优良级占33%,较差等级主要分布在中东部经济社会发达地区。土壤有机碳研究表明,全国表层土壤(0～0.2m)平均碳密度仅为3 186t/km2,且各地区碳密度变化幅度较大,说明中国土壤有机碳处于低水平和不稳定状态。"十一五"期间勘查地球化学针对重大资源与环境问题,深化和延拓地质工作内涵,逐步形成矿产资源评价、生态地质科学研究、土地质量与生态评价、全球变化科学研究及基础地学研究等现代地质工作若干重要发展领域。     

全国地球化学基准网建立与土壤地球化学基准值特征

全球一致性和权威性地球化学观测数据是资源与环境评价的定量标尺。中国实施的"全国地球化学基准计划"作为"全球地球化学基准计划"的一部分,于2008—2014年实施,建立了覆盖全国的地球化学基准网。按照1∶20万图幅为网格单元,在全国1600个网格单元中,共部署3382个汇水域采样基准点,每个基准点同时采集了表层和深层土壤样品,共计采集6617件样品,使用高精度分析技术和严格的质量控制,分析了81个地球化学指标。本文首次给出了全国土壤81个指标地球化学基准值数据,初步阐释了地球化学基准值数据和空间分布特征与地质背景、成矿作用、表生作用以及人类活动的关系。     

大兴安岭成矿带大型银多金属矿区域地球化学预测指标

如何利用地球化学填图数据来预测大型矿是当前面临的一个重要课题。文中利用大兴安岭地区1∶20万区域化探扫面数据和1∶100万中蒙边界地球化学填图数据进行综合研究。发现1∶100万地球化学编图圈定的地球化学省与矿集区存在十分密切的关系,1∶20万地球化学编图圈定的区域地球化学异常与大型矿存在对应关系。以大兴安岭3个大型银铅锌矿为例建立了预测大型矿的地球化学指标。大型银多金属矿具有Pb、Zn、Ag 等3个以上元素异常在空间上相套合;异常具有3层以上套合结构,即地球化学省（>500 km2）包裹区域异常（>100 km2）,区域异常包裹局部浓集中心（n×10 km2）;标准化综合异常下限大于4.5,异常衬度大于2.0。     

Relationships between geochemistry of basal till and chemistry of surface soil at forested sites in Finland

Concentrations of several elements extractable with BaCl₂ and acid ammonium acetate (pH 4.65) were measured in the organic and 4 mineral soil layers on the national forest inventory plots of the Finnish Forest Research Institute. The soil data also includes total concentrations of elements in the organic layer and site and soil physical characteristics. Data were compared with the aqua regia extractable element concentrations measured in the nationwide regional till geochemical mapping carried out by the Geological Survey of Finland.Correlations between concentrations in surface soil and underlying basal till were generally highest for K, Mg, Mn, P and Zn; in the organic layer and till they were highest for Cr and Cu. The strength of these correlations did not increase regularly from surface to deeper soil layers. All soil base cations with the exception of Ca, which is of relatively low solubility, were well correlated. The elements Zn, K, P, Al and Mn in till were the most reliable indicators of surface soil chemistry.Fuzzy clustering showed that the correlation between element concentrations in basal till and the two uppermost layers of mineral soil was better within areas of distinct till geochemistry, such as the schist belts in southwestern Finland, the Lake Ladoga–Bothnian Bay zone and the Kuusamo schist belt.Surface soil chemical variables were clearly better in discriminating fertility classes of forest sites than were element concentrations in basal till. The independent ability of till geochemistry to distinguish these productivity classes and to explain surface soil fertility was nevertheless demonstrated.     

Geological factors affecting the distribution of trace metals in glacial sediments of central Newfoundland

 In central Newfoundland (NTS 12A/10, 15, 16, 2H/1), As, Pb, and Zn concentrations in the clay-sized (<0.002 mm) and silt and clay-sized (<0.063 mm) fractions of till reflect compositional differences among and within rock terranes at scales of kilometers to tens of kilometers. In those fractions, till derived from volcanic bedrock of Victoria Lake Group (Tulks Hill) is notably enriched in As (50–>1000 ppm), exceeding levels commonly set for purposes of environmental protection. Near Pb-Zn mines at Buchans, geochemical variation with depth reflects the dispersal of detritus from mineralized bedrock, and differences in sediment type and provenance. There, surface sediments are rich in granitic debris derived from the Topsails igneous terrane 5 km north of Buchans and contain low concentrations of trace metals. These sediments are compositionally unrelated to either Buchans Group volcanic rock or an underlying, older till enriched in sulphide minerals and trace metals. Metal-rich till extending up to 10 km southwest of Buchans results from combined glacial and debris flow transport related to two distinct geological events. Trace metals are enriched (two- to fourfold) in the clay-sized fraction of till compared to the silt and clay-sized, and are associated with Al- and Mg-bearing minerals that preferentially concentrate in the clay fraction. The geochemistry of the silt and clay-sized fraction can approximate that of the <2-mm fraction. Background variations in till illustrate the important role of a geological framework to the interpretation of geochemical surveys and the origins of trace metals in the environment. Received: 31 October 1996 · Accepted: 27 May 1997     

Effect of widespread severely acidic soils on spatial features and abundance of trace elements in streams

In the coastal area of western Finland, a large number of streams are strongly acidic and contaminated with metals. The reason for this is not historical and present industrial, mining and urban activities, but a current high rate of weathering and leaching of widespread acid sulphate soils (pH 2.5–4.0) developed in artificially drained Holocene marine and lacustrine sulphide-bearing sediments. Evaluation of existing hydro- and geochemical field and experimental data revealed that: (1) cobalt, Ni and Zn are extensively leached from the acid sulphate soils and thus exist abundantly in streams affected by such soils, (2) copper and Tl are also leached abundantly from the acid sulphate soils, although not to the same extent as are Co, Ni and Zn, (3) vanadium is in general depleted and Cr only weakly enriched in streams draining ‘the average acid sulphate soil’, but they increase substantially in severely acidic streams in catchments underlain with particularly acidic soil, (4) arsenic and Pb are not leached more abundantly from the acid sulphate soils than from the common types of soils and sediments (till, glaciofluvial deposits, peat) resulting in aquatic abundance and distribution patterns unrelated to the acid sulphate soil occurrences.     

Geochemical evidence for a brooks range mineral belt, Alaska

Geochemical studies in the central Brooks Range, Alaska, delineate a regional, structurally controlled mineral belt in east—west-trending metamorphic rocks and adjacent metasedimentary rocks. The mineral belt extends eastward from the Ambler River quadrangle to the Chandalar and Philip Smith quadrangles, Alaska, from 147° to 156°W. longitude, a distance of more than 375 km, and spans a width from 67° to 69°N. latitude, a distance of more than 222 km. Within this belt are several occurrences of copper and molybdenum mineralization associated with meta-igneous, metasedimentary, and metavolcanic rocks; the geochemical study delineates target areas for additional occurrences.A total of 4677 stream-sediment and 2286 panned-concentrate samples were collected in the central Brooks Range, Alaska, from 1975 to 1979. The −80 mesh (< 177 μm) stream sediment and the heavy (specific gravity > 2.86) nonmagnetic fraction of the panned concentrates from stream sediment were analyzed by semiquantitative spectrographic methods.Two geochemical suites were recognized in this investigation; a base-metal suite of copper-lead-zinc and a molybdenum suite of molybdenum-tin-tungsten. These suites suggest several types of mineralization within the metamorphic belt. Anomalies in molybdenum with associated Cu and W suggest a potential porphyry molybdenum system associated with meta-igneous rocks. This regional study indicates that areas of metaigneous rocks in the central metamorphic belt are target areas for potential mineralized porphyry systems and that areas of metavolcanic rocks are target areas for potential massive sulfide mineralization.     

基于地球化学基线的土壤重金属污染潜在生态风险评价

地球化学基线是区分地球化学背景和异常的重要参数。在采集和测试德兴地区约5000km^2面积的479个表层土壤样品基础上，采用标准化方法确定了样品中Cu，Pb，Zn，Cd，Cr，As和Hg等7种重金属元素的基线值，并以基线作为潜在生态风险评价的参比值，对德兴地区土壤重金属污染进行潜在生态风险评价。结果表明：研究区可划分为3个潜在生态风险等级：轻微生态风险、中等生态风险和强生态风险，强生态风险区主要分布在德兴铜矿和钟家山煤矿等矿业活动区附近。其他大部分地区为轻微生态风险区。     

The chemical and physical characteristics of heavy metals in humus and till in the vicinity of the base metal smelter at Flin Flon, Manitoba, Canada

 Trace element geochemistry of humus (<0.425 mm) and till (<0.002 mm) collected in the Flin Flon-Snow Lake area, northern Manitoba and Saskatchewan, provides a regional context for assessing smelter contamination in the environment. The area includes a Cu-Zn smelter known to discharge As, Cd, Cu, Fe, Hg, Pb, and Zn. In this study, sequential extraction analyses, scanning electron microscopy and x-ray diffraction analyses were used on a suite of samples to determine: (1) the chemical and physical characteristics of heavy metals in surficial sediments related to distance from the smelter, (2) criteria for assessing the relative contribution of these metals from natural and anthropogenic sources, and (3) the potential of these metals for remobilization in the environment. Humus geochemistry reflects the anthropogenic and natural component of heavy metal concentrations. Smelter-related elements show anomalously high values adjacent to the smelter, decreasing with distance until background values are reached at 70–104 km, depending on the element. In humus, Zn is associated primarily with labile phases; Hg with non-labile phases. Adjacent to the smelter, high proportions and concentrations of Zn and Hg in non-labile phases, indicative of smelter-derived particulates, are confirmed by SEM examination. The particles occur as spheres, irregular grains, and with organics. With increasing distance from the smelter, the geochemical response to bedrock composition is more obvious than the anthropogenic input. Till geochemistry reflects the natural variation imposed by bedrock composition. At highly contaminated sites (<3 km from the smelter), increased percentages of smelter-related elements in labile phases suggests heavy metals are leached from humus to the underlying sediment. Received: 5 November 1996 · Accepted: 31 March 1997