Effect of agricultural land use on the chemistry of groundwater from basaltic aquifers, Jeju Island, South Korea

Geochemical processes were identified as controlling factors of groundwater chemistry, including chemical weathering, salinization from seawater and dry sea-salt deposition, nitrate contamination, and rainfall recharge. These geochemical processes were identified using principal component analysis of major element chemistry of groundwater from basaltic aquifers in Jeju Island, South Korea, a volcanic island with intense agricultural activities. The contribution of the geochemical processes to groundwater chemistry was quantified by a simple mass-balance approach. The geochemical effects due to seawater were considered based on Cl contributions, whereas the effects due to natural chemical weathering were based on alkalinity. Nitrogenous fertilizers, and especially the associated nitrification processes, appear to significantly affect groundwater chemistry. A strong correlation was observed between Na, Mg, Ca, SO₄ and Cl, and nitrate concentrations in groundwater. Correspondingly, the total major cations, Cl, and SO₄ in groundwater were assessed to estimate relative effect of N-fertilizer use on groundwater chemistry. Cl originates more from nitrate sources than from seawater, whereas SO₄ originates mostly from rainwater. N-fertilizer use has shown the greatest effect on groundwater chemistry, particularly when nitrate concentrations exceed 6–7 mg/L NO₃–N. Nitrate contamination significantly affects groundwater quality and 18% of groundwater samples have contamination-dominated chemistry.     

Distribution of arsenic and other minor trace elements in the groundwater of Ischia Island (southern Italy)

The island of Ischia belongs to the active volcanic area of Naples. It is formed from Quaternary volcanic rocks and exhibits intense hydrothermal activity, which is manifested through numerous springs, fumaroles and sporadic geysers. The content of minor and trace elements in groundwater has been analyzed, including some elements that are considered toxic for humans. Mean concentrations of As, B, Fe, Mn, Sb, and Se in samples from 43 aquifer points exceed the WHO recommended values and the limits set by European and Italian legislation (98/83/CE and DM 471, respectively). In general, the spatial distribution of the elements follows a common pattern: it is governed by a marked structural control, which favors hydrochemical processes that liberate the elements into the water.     

兖州矿区煤中某些微量元素的赋存状态研究

微量元素的赋存状态决定其在煤的加工利用过程中释放的难易程度和毒性，弄清其在煤中的赋存状态，对准确评价元素的工艺性能、环境影响、作为副产品的可能性以及在地质意义上都是十分重要的。分析了微量元素在煤中的有机亲合性，采用数理统计方法，求得了微量元素与煤中有机显微组分、三态硫、灰分之间的相关性，并在浮沉实验的基础上，分析了微量元素的存在状态，通过研究向知，Ge、Ga、U、V、Cu、Th、Pb和Zn主要以无机态存在于煤中，F和Cl可能以有机态存在为主，As无机态和有机态存在的机率相似。     

Source and mobility of minor and trace elements in a volcanic aquifer system: Mt. Vulture (southern Italy)

In this paper we provide a geochemical investigation on 34 groundwater samples in the Mt. Vulture volcanic aquifer representing one of the most important groundwater resources of the southern Italy pumped for drinking and irrigation supply. The present study includes the first data on the abundance and mobility of minor and trace elements and the thermodynamic considerations on water–rock interaction processes in order to evaluate the conditions of alkali basalt weathering by waters enriched in magma-derived CO₂. The results highlight the occurrence of two hydrofacies: bicarbonate alkaline-earth and alkaline waters deriving from low-temperature leaching of volcanic rocks of Mt. Vulture, and bicarbonate-sulfate-alkaline waters (high-salinity waters) related to prolonged water circulation in alkali and feldspathoids-rich pyroclastic layers interbedded with clay deposits. The Al-normalized relative mobility (RM) of metals in Vulture's aquifer varies over a wide range (10^− 1 < RM < 10⁴), confirming that the basalt weathering is not a congruent and isochemical process. Chemical equilibrium studies show that the bicarbonate alkaline-earth and alkaline waters, having a short interaction with silicate minerals, plot very close to the kaolinite–smectite stability boundary, whereas the high-salinity waters fall in the stability field of smectite and muscovite because of prolonged interaction with alkali and feldspathoids-rich pyroclastic layers. Overall, for the bicarbonate alkaline-earth and alkaline waters, the release of toxic metals in solutions is related to the spatial variation of host-rock geochemistry, the high-salinity waters, collected near urban areas, show values higher than legal limits for Ni and As, likely as a consequence of anthropogenic contribution.     

Salinity mapping of coastal groundwater aquifers using hydrogeochemical and geophysical methods: a case study from north Kelantan,Malaysia

Integrated hydrogeochemical and geophysical methods were used to study the salinity of groundwater aquifers along the coastal area of north Kelantan. For the hydrogeochemical investigation, analysis of major ion contents of the groundwater was conducted, and other chemical parameters such as pH and total dissolved solids were also determined. For the geophysical study, both geoelectrical resistivity soundings and reflection seismic surveys were conducted to determine the characteristics of the subsurface and groundwater contained within the aquifers. The pH values range from 6.2 to 6.8, indicating that the groundwater in the study area is slightly acidic. Low content of chloride suggests that the groundwater in the first aquifer is fresh, with an average concentration of about 15.8 mg/l and high geoelectrical resistivity (>45 ohm m). On the other hand, the groundwater in the second aquifer is brackish, with chloride concentration ranging from 500 mg/l to 3,600 mg/l and very low geoelectrical resistivity (<45 ohm m) as well as high concentration of total dissolved solids (>1,000 mg/l). The groundwater in the third aquifer is fresh, with chloride concentrations generally ranging from 2 mg/l to 210 mg/l and geoelectrical resistivity of greater than 45 ohm m. Fresh and saltwater interface in the first aquifer is generally located directly in the area of the coast, but, for the second aquifer, both hydrogeochemical and geoelectrical resistivity results indicate that the fresh water and saltwater interface is located as far as 6 km from the beach. The considerable chloride ion content initially suggests that the salinity of the groundwater in the second aquifer is probably caused by the intrusion of seawater. However, continuous monitoring of the chloride content of the second aquifer indicated no significant changes with time, from which it can be inferred that the salinity of the groundwater is not affected by seasonal seawater intrusion. Schoeller diagrams illustrate that sulphate concentrations of the groundwater of the second aquifer are relatively low compared to those of the recent seawater. Therefore, this result suggests that the brackish water in the second aquifer is probably from ancient seawater that was trapped within the sediments for a long period of time, rather than due to direct seawater intrusion.     

新疆金矿火山岩微量及稀土元素地球化学特征

金矿火山岩微量元素以Th和Zr的明显正异常及Nb和Ti的明显负异常为特征。微量元素比值蛛网图模式曲线均呈微向左倾斜的多峰多谷曲线。过渡元素以Cr和Ni的明显负异常及Sc,Co,Cu明显正常为特征。过渡元素球粒陨石标准化曲线，也均呈微向右倾斜的W形曲线。稀土元素以稀土总量偏低，轻稀土富集，重稀土亏损，Eu具微弱异常至微弱正常为特征。稀土元素配分模式均呈微向右倾斜和近于水平的平滑曲线，陆相火山作用两类成矿岩浆建造－陆相火山岩与潜火山杂岩具有基本一致的微量元素和稀土元素地球化学特征。     

Determination of major and trace elements in sphalerite using laser ablation double focusing sector field ICP-MS

The analytical performance of laser ablation (LA) for the determination of Co, Fe, Cd, Ag, Mn, Cu and S in sphalerite was evaluated using double focusing sector field inductively coupled plasma mass spectrometry (ICP-SFMS). Samples were collected from Zinkgruvan, situated in the south central Sweden. The use of Zn for internal standardisation, together with correction for FeS impurities in sphalerite, allows straightforward quantification without using external methods for the determination of the actual Zn content. LA–ICP-SFMS results were compared with data obtained by conventional pneumatic nebulisation introduction of sample solutions following acid digestion. Good agreement between the two methods was obtained for homogeneously distributed elements. For the majority of the elements under consideration, LA–ICP-SFMS precision was better than 10% RSD.     

淮南张集矿区煤中微量元素的含量分布特征分析

在采用ICP-AES对张集7个煤层144个样品微量元素含量测试分析的基础上,探讨了元素在不同煤层中的变化规律及其在煤层对比中的应用。结果表明:张集矿区煤中元素B、Se和As含量偏高;不同煤层中微量元素含量变化较大,但具有一定的规律性,其中在9煤层中元素Ba和Cr含量最低,Mn、Zn、As和Se含量相对较高,可以利用这些元素分布特征来区别和划分相邻煤层。     

Influence of trace element fluxes from submarine groundwater discharge (SGD) on their inventories in coastal waters off volcanic island,Jeju, Korea

The concentrations of trace elements in groundwater and seawater were measured in a coastal embayment (Bangdu Bay) of a volcanic island (Jeju) off the southernmost coast of Korea in August and December of 2009. The concentrations of trace elements (Al, Mn, Fe, Co, Ni, and Cu) in the groundwater in summer were approximately 20-fold higher than those in winter, with good correlation to each other. Overall, the concentrations of most of the trace elements in the groundwater were 3- to 70-fold higher than those in the seawater of this Bay. Simple budget calculations showed that large fluxes of submarine groundwater discharge (SGD)-driven trace elements were responsible for the unusually enhanced concentrations of trace elements (particularly for Al, Fe and Co) in the summer seawater. The results imply that the temporal changes in SGD-driven trace element fluxes are large and may contribute considerably to the budget of trace elements in the coastal ocean, particularly off a highly permeable volcanic island.     

河北下堡基性岩墙地球化学特征及源区性质

通过对河北后城基性岩墙进行系统研究,SiO2=47.07％～50.28％,(Na2O+K2O)在2.83％～3.75％之间变化.具有明显的轻稀土元素富集 ((La/Yb)N=4.40～4.86)和大离子亲石元素(Rb、Th和U等)富集现象,亏损高场强元素Nb和Ta.地球化学特征表明,岩墙产于板内拉张的构造环境,经过了橄榄石、单斜辉石、角闪石和黑云母等矿物的分离结晶作用.对La/Sm、Ta/La、Nb/La的分析表明,本区岩浆在上升过程中受到地壳物质的混染作用影响不明显,岩墙的源区与深俯冲作用引起的地幔交代作用有关.通过对微量元素及稀土元素比值的研究证明,基性岩墙源区为过渡型地幔源区,岩墙的母岩浆来自石榴子石二辉橄榄岩地幔,主要经历了石榴石+尖晶石二辉橄榄岩部分熔融,熔融程度在10％～20％之间,岩浆的起源深度在75kin左右.     

Use of major and selected trace elements to describe mixing processes in a water reservoir

Data on temperature, major constituents and some trace elements, measured in the dissolved and particulate phases, were used to identify the hydrodynamics of a reservoir (the Bicaz reservoir, Romania). Results revealed that the reservoir experiences two thermal stratifications per year (summer and winter). However, the summer stratification is delayed by the high river inflow of June–July. Two layers were identified, a surface and a deep layer, whose location and impact vary with time. The surface layer originates from the river inflow (intrusion layer) and the deep current is produced by the outflow (velocity current). According to season, the river inflow either supplies the deep current or remains recordable up to the dam. Consequently, the structure of the water column, and thus the biogeochemical processes within it, are governed both by thermal stratification and by these layers.     

Occurrence and migration of hazardous trace elements in coals from Guizhou Province, China

Coals from Guizhou Province, Southwest China, attract many researchers＇ attention for their high concentrations of hazardous trace elements, sulphur and mineral components. Trace elements in coals have diverse modes of occurrence that will greatly influence their migration in the process of coal preparation. Mode of occurrence is also important in determining the partitioning during coal combustion. The coal floatation test by progressive release was used to study the migration of trace elements and mineral components in the process of froth floatation. Inductively coupled plasma mass spectrometry （ICP-MS） was used to determine the absolute concentrations of trace elements including As, Be, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sb, Se, Th, U, V and Zn in the parent coals and the floatation fractions. Precise determination of the mineral matter percentage in coals was obtained by low-temperature ashing. The mineral compositions in coals were quantified using Rietveld-based X-ray diffraction analysis package on low-temperature ash. Scanning electron microscope equipped with energy dispersive X-ray detector was used to provide information on the forms of occurrence of mineral components in coal. Five floatation fractions were obtained from the pulverized coal samples. The contents of trace elements and mineral components decrease from the first tailings to the last cleaned coal. The concentrations of trace elements and mineral components in parent coals and different floatation samples show that trace elements and mineral components are mainly concentrated in the first tailings samples. Nearly 60% of mineral components are enriched in the first tailings, whereas less than 1.3% remains in the cleaned coal. The ratio of sixteen trace elements concentrations in the first tailings to the corresponding concentrations in the cleaned coal ranges from 1.6 to 22.7. Quantitative mineralogical analysis results using the full-profile general structure analysis system （GSAS） showed that the main compositions of LTA include quartz, calcite, kaolinite, pyrite, chlorite, montmorillonite, illite, anatase and pyrite.     

Mineral matter and trace elements in coals of the Gunnedah Basin, New South Wales, Australia

The concentrations of major and trace inorganic elements in a succession of Permian coals from the Gunnedah Basin, New South Wales, have been determined by X-ray fluorescence techniques applied to both whole-coal and high-temperature ash samples. The results have been evaluated in the light of quantitative data on the minerals in the same coals, determined from X-ray diffraction study of whole-coal samples using a Rietveld-based interpretation program ( ™), to determine relationships of the trace elements in the coals to the mineral species present. Comparison of the chemical composition of the coal ash interpreted from the quantitative mineralogical study to the actual ash composition determined by XRF analysis shows a high degree of consistency, confirming the validity of the XRD interpretations for the Gunnedah Basin materials. Quartz, illite and other minerals of detrital origin dominate the coals in the upper part of the sequence, whereas authigenic kaolinite is abundant in coals from the lower part of the Permian succession. These minerals are all reduced in abundance, however, and pyrite is a dominant constituent, in coals formed under marine influence at several stratigraphic levels. Calcite and dolomite occur as cleat and fracture infillings, mostly in seams near the top and bottom of the sequence. The potassium-bearing minerals in the detrital fraction are associated with significant concentrations of rubidium, and the authigenic kaolinite with relatively high proportions of titanium. Zirconium is also abundant, with associated P and Hf, in the Gunnedah Basin coal seams. Relationships exhibited by Ti, Zr, Nd and Y are consistent with derivation of the original sediment admixed with the seams from an acid volcanic source. Pyrite in the coals is associated with high concentrations of arsenic and minor proportions of thallium; no other element commonly associated with sulphides in coals, however, appears to occur in significant proportions with the pyrite in the sample suite. Small concentrations of Cl present in the coal are inversely related to the pyrite content, and appear to represent ion-exchange components associated with the organic matter. Strontium and barium are strongly associated with the cleat-filling carbonate minerals. Ge and Ga appear to be related to each other and to the coal's organic matter. Cr and V are also related to each other, as are Ce, La, Nd and Pr, but none of these show any relationship to the organic matter or a particular mineral component.     

Migration and contamination of major and trace elements in groundwater of Madras city,India

Groundwater samples collected from both open and bore wells in an area of about 270 km² from Madras City, India, have been analyzed for major ions (HCO₃, Cl, Si, Na, Ca, and Mg) and trace elements (As, Se, B, V, Cr, Fe, Co, Pb, Cu, Zn, Cd, Mn, Ni, Mo, and Ba). The study reveals that the quality of potable water has deteriorated to a large extent. Seawater intrusion into the aquifer has been observed in nearly 50 percent of the study area. The toxic elements (As and Se) have already exceeded the maximum permissible limits of drinking water in almost the entire city. A positive correlation of As and Se with other toxic metals such as V, Cr, Fe, B, etc., indicates that all these elements are anthropogenic in origin. Applying multivariate analysis, the source for trace elements in groundwater has been grouped into two major factors: pollution and mobilization factors. The groundwater in the study area is largely contaminated by organic effluents and reflects the intensity of pollution caused by the overlying soil sediment and rapid infiltration of the pollutants.     

西藏巴达铜金矿床黄铁矿原位主微量元素特征及其环境效应

黄铁矿在自然环境中极易发生氧化,造成严重生态环境问题。为了研究自然条件下不同粒度和晶形黄铁矿化学成分的差异对黄铁矿氧化速率的影响,本文对巴达铜金矿床黄铁矿进行了LA- ICP- MS原位主微量元素分析和矿物面扫描分析。测试结果表明粗粒黄铁矿S、Fe含量较高,成分更纯;微量元素As、Co、Ni和Pb、Cu、Zn分别以类质同象方式和包裹体形式更多地存在于细粒黄铁矿中,二者均能促使细粒黄铁矿氧化速率加快;粗粒黄铁矿中Cr和Ti元素含量较高,其氧化后生成致密氧化膜可抑制黄铁矿被进一步氧化。本文认为对于本矿床中粗粒黄铁矿和细粒黄铁矿氧化污染问题应采用两种不同的治理措施,对于不易被氧化的粗粒黄铁矿,使其处于常温常压的干燥避光环境中即可防止发生氧化;对于易氧化的细粒黄铁矿,其氧化产物造成污染对环境压力较大,应采用源头治理和末端治理相结合的措施进行处理,以达到更科学的治理效果。     

Impacts of land use change and groundwater management on long-term nitrate-nitrogen and chloride trends in groundwater of Jeju Island,Korea

Impacts of land use changes and groundwater management actions on groundwater quality were evaluated at the island scale with spatiotemporal trends of NO₃-N and Cl concentrations in groundwater of Jeju Island, Korea. The temporal trends from 1993 to 2012 in the concentrations of NO₃-N and Cl from more than 3900 wells were estimated using the Mann–Kendall trend test and Sen’s slope analysis and compared with the land use change trend for the period 1995–2009. The results indicate that the upward trends in NO₃-N were associated with the expansion of agricultural lands, whereas Cl trends were considered to be affected by other factors in addition to the land use changes. In the mid-mountainous region, the deterioration in the groundwater quality by the both NO₃-N and Cl was expected due to the continuous expansion of agricultural lands. In the lowland area, the NO₃-N and Cl components showed different trends depending on the regions. In the eastern area, increasing trends in NO₃-N were observed due to the development of new agricultural areas, while the Cl concentration was observed to decrease as a result of the regulation on groundwater extraction to reduce seawater intrusion. Our study highlights that a comprehensive interpretation of trends in NO₃-N and Cl and land use changes for long-term periods can provide useful insights to prepare for suitable groundwater management plans in the whole island perspective.     

内蒙古黄岗梁铁锡矿床闪锌矿LA-ICP-MS微量元素组成及其指示意义

黄岗梁铁锡矿床位于大兴安岭中南段晚古生代增生造山带。矿区内闪锌矿产于矽卡岩中,可分为浸染状和层纹状闪锌矿。本文对两种闪锌矿进行了高精度LA-ICP-MS元素含量测试,结果表明矿区两种闪锌矿具有相同成因特征,闪锌矿中Mn、Cu、As、In较富集,Ga、Ge、Cd含量较低,而As、Sn、Bi、Pb含量变化较大。Cu、Sn、Bi、Pb等元素在闪锌矿中以独立矿物赋存,Mn、Fe、Ga、Ge、Cd、In、Sb以类质同像形式赋存在闪锌矿晶格中。In/Ga、In/Ge比值较低,Zn/Cd比值为233~250,指示闪锌矿形成于中高温环境。Cd/Fe、Cd/Mn比值分别小于0.1和0.5,指示闪锌矿成因与岩浆活动有关,In Ge特征图解也指示其矽卡岩成因。通过与国内外典型矿床闪锌矿微量元素特征对比,结合矿床地质特征认为黄岗梁铁锡矿床中闪锌矿属于与燕山期岩浆作用有关的中高温矽卡型闪锌矿。     

磁铁矿中微量元素和铂族元素的组成特征

文章分析了磁铁矿中铂族元素(PGE)含量的特征,发现磁铁矿中铂族元素富集为10-9级,主要为PPGE(即Pd,Pt,Rh)。富集PPGE的主要原因是其在热液活动的晚期阶段可以被轻微的再分配和富集,其含量的高低严格受岩浆结晶过程中氧逸度的控制。磁铁矿的结晶程度直接影响岩浆体系的氧逸度,控制了PGE的含量分布,进而影响成矿。     

淮北煤中几种具有环境意义的微量元素分布

通过中子活化法,对淮北煤田主采煤层中和相对应的灰中几种具有环境意义的微量元素含量进行了测试,分析了它们在煤中和灰中的含量分布,并与中国和华北煤田煤中的平均值进行了对比,以便为煤和煤灰的综合利用提供基础资料。     

Trace elements distribution in stream sediments of an abandoned U mining site in the Eastern Carpathians,Romania, with particular focus on REEs

Trace elements distribution, including rare earth elements (REEs), in stream sediments of an abandoned U mining site in the Eastern Carpathians, Romania, were of high concern of interest in the present work. A total number of 40 riverbed sediments samples collected from the Bistricioara River and local tributaries (Primatar, Bradul, Prisacani, Barasau, Grintiesul Mare and Valea Seaca) were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) and energy dispersive X-ray fluorescence spectrometry (XRF). All REEs including La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu were identified and quantified in the present work using ICP-MS technique. For other 24 elements (Ti, V, Cr, Co, Zn, Li, Be, Rb, Sr, Y, Sc, Zr, Nb, Sb, Ba, Ta, W, Pb, U, Ni, Cu, Mo, As, Th) similar information was obtained either by ICP-MS or XRF techniques. The impact and the relevance of the obtained data base might be significant at a local scale of about 50 km².Enrichments of some trace elements of interest in comparison to the upper continental crust allowed discrimination between various mineralization processes specific for the investigated areas. Uranium mineralization and Paltin-type (Pb, Zn) mineralization seems to be specific for the NW area of the investigated region. Negative anomaly characteristic for the upper crustal rocks was identified for Eu and Ce elements. Evidences were obtained also for the existence of ultramafic rocks (Ni, Cr, Co and V) in the investigated riverbed sediments. The observation was also confirmed by the binary plots analysis of Th/Cr vs. Th/Co and Cr/V vs. Y/Ni pairs. From the investigated tributaries to Bistricioara River, Barasau seems to exert the highest influence on the abundances of REEss in the entire area. Most probably some chemical parameters such as the pH of the water streams influence leaching and depletions of some chemical constituents in various minerals specific for the region.The existence of magnetite, garnets, pyrite and sillimanite minerals was confirmed by SEM-EDAX and XRF analysis, as well by optical microscopy. Principal Component Analysis runs confirmed the association of some chemical elements in the riverbed sediments in close connection with the minerals from which they originate.The present work reports for the first time upon the authors knowledge clear scientific evidence and chemical information concerning the geology and geochemistry, i.e. transition metals, high field strength elements, alkali and alkaline earth elements, rare earth elements (REEs) and others, in stream sediments crossing the Tulghes-Grinties mining area (Eastern Carpathians, Romania). For the analysed REEs this is the first study reporting consistent information on the concentrations of the entire array of both light REEs (six elements) and heavy REEs (ten elements) in Bistricioara Basin stream sediments. Relevant scientific data related to geochemical characteristics of ultramafic rocks existent in the investigated area were also generated. Moreover, data reported in the present work might be considered as a reference geochemical database relevant for the investigated area, which can be used as a trustworthy input for a systematic national geochemical atlas.