Groundwater Pollution by Heavy Metals in Historical Mining Area of Lavrio,Attica, Greece

This article deals with the impacts of past mining activities andinefficient water resources management on groundwater quality inthe Lavrio area. Thirty-three water samples were collectedduring March 1998 and were analyzed for major ions (Ca, Mg, Na,K, HCO₃, Cl, NO₃, SO₄, PO₄), trace elements(Fe, Pb, Ni, Zn, Mn, Cu, Cr, Cd) and water parameters (Temperature,pH, conductivity, hardness and SiO₂). High concentrationsof heavy metals (lead, cadmium, zinc, nickel) are recorded ingroundwater samples in the Lavrio area. The highestconcentrations are recorded in the unconfined aquifer (alluvialdeposits and schists), due to mining activities. Qualitydeterioration of groundwater is also decumented and attributedto seawater intrusion and nitrate pollution of agriculturalorigin. The data were subjected to simple correlation analysisand R-mode factor analysis in order to examine the relationshipsbetween the parameters. There is a relationship between theelements participating in the sulfide (Pb, Zn, Cu, Cd) andiron-manganese mineralization and a strong relationship betweenNi–Cr. In the factor analysis a four-factor model is suggested,which can explain 72.5% of the total variance. The contributionof each factor at every site is also computed and maps showingthe geographical distribution are illustrated. The areas withhigh concentrations of heavy metals are defined from these maps.     

Assessment of Heavy Metal Bioavailability in Contaminated Soils from a Former Mining Area (La Union, Spain) Using a Rhizospheric Test

A rhizospheric biotest, consisting of a thin layer of substratum in close contact with roots of Lolium multiflorum, was used on two contrasting contaminated soils (Cabezo and Brunita) issued from a former mining area in La Union (Spain). On top of this biotest, soil characterisation, including CaCl₂ selective extractions, was performed. Total heavy metal concentrations were the highest in the soil from Cabezo, but CaCl₂ extractions indicated higher heavy metal mobilities in Brunita soil. On the base of heavy metal concentrations and biomass production in L. multiflorum seedlings, availability assessed by the rhizospheric biotest was higher than the values obtained from CaCl₂ extraction, except for Mn and Pb. Rhizospheric biotest also revealed higher heavy metal bioavailability for Cabezo. The low pH of Brunita (3.47) could explain the high CaCl₂-extractable heavy metal concentrations as well as the high transfer factor found for Cu, Mn and Zn in this substrate. Cu, Mn and Zn toxicities were also detected for shoot tissues. Transpiration rates were clearly lower for seedlings exposed to Brunita than for those exposed to Cabezo, while water use efficiency was higher for the former (4.8 mg?DW?ml^?1) than for the latter (3.8 mg?DW?ml^?1). Iron nutrition was found to interfere with heavy metal root absorption, mainly through negative interactions during root absorption. It is concluded that rhizospheric test offers the advantage to consider the root?Csoil interactions in a dynamic perspective and constitutes a useful tool for the assessment of heavy metal availability on contaminated soils. Heavy metal bioavailability assessment should not be based on only one measure alone, but on different and complementary approaches.     

高潜水位矿区不同复垦方式下土壤热导率及其影响因素

以东部高潜水位采煤塌陷复垦耕地为研究对象,研究挖深垫浅复垦、充填复垦、预复垦3种复垦方式下土壤热导率的分布及原因。在3种复垦方式典型样地上开挖剖面,分别取0—20,20—40,40—60cm土层土样,经实验分析观测土壤热导率及相关物理指标。结果表明:(1)复垦方式、剖面层次和二者交互作用均是使热导率产生显著差别的因素(p0.01),对土壤热导率总体变异的贡献率分别为86.8%,89.6%,71.9%;(2)土壤热导率随土壤剖面深度增加呈先增加后降低的型变化趋势;(3)复垦可以显著(p0.05)影响土壤热导率大小,并增加其在不同剖面层次上分布的差异;(4)在含水量和温度差异不大的条件下,土壤容重在1.205~1.593g/cm3时,砂粒含量为影响热导率的主要因素,当土壤容重在1.604~1.813g/cm3时,容重为影响热导率的主要因素。与未塌陷耕地相比,复垦土壤热导率偏低,在土层间分布差异性增加,因此应综合考虑容重和质地,从降低土壤容重的角度入手,改良复垦土壤热导率。     

Sulfate Reduction in a Lake and the Groundwater of a Former Lignite Mining Area Studied by Stable Sulfur and Carbon Isotopes

Water, Air, &; Soil Pollution - The isotopic and chemical composition of water and dissolved sulfur and carbon compounds from a flooded lignite-mining lake and a dump site in Central Germany...     

Arsenic Contamination in Soils Affected by a Pyrite-mine Spill (Aznalcóllar, SW Spain)

On 1998, a settling pond of a pyrite mine in Aznalcóllar (SW Spain) broke open, spilling some 3.6?×?10⁶ m³ of water and 0.9?×?10⁶ m³ of toxic tailings into the Agrio and Guadiamar river basin 40 km downstream, nearly to Doñana National Park. The soils throughout the basin were studied for arsenic pollution. Almost all the arsenic penetrated the soils in the solid phase (tailings) in variable amounts, mainly as a result of the different soil structure. The chemical oxidation of the tailings was the main cause of the pollution in these soils. A study of the relationships between the main soil characteristics and arsenic extracted with different reagents (water, CaCl₂, acetic acid, oxalic–oxalate and EDTA) indicates a direct relationship with the total arsenic concentration. The highest amount of arsenic was extracted by oxalic–oxalate (24%–36% of the total arsenic), indicating the binding with the iron oxides.     

River Water Metal Speciation in a Mining Region – The Influence of Wetlands,Liming, Tributaries,and Groundwater

Changes in metal speciation occurring along the river Vormbäckenhave been investigated, and the potential for using such changes to reduce metal transport to areas further downstream has been evaluated.Vormbäcken is situated in a mining region in northern Sweden. Catchment area features likely to influence metal speciation include wetlands situated along the river, addition of treated (liming) effluent water from a mine area, and addition of other surface waters and groundwater. Surface water samples were collected from seven stations along the river on six occasions, representing different flow regimes. The total As, Ca, Cd, Cu, Fe, Pb, and Zn concentrations in the samples were partitioned into particulate (>0.4 μm and 0.2–0.4 μm, or only >0.2 μm) and dissolved (<0.2 μm, either associated with organiccarbon, or as free metal ions and inorganic complexes) fractions by means of filtration and an ion-exchange technique. The most important finding is that, with the exception of Ca, the fraction of particulate bound metals increased with increasing concentrations of particulate Fe. This Fe has its origin in surface waters and groundwater that join the river on its way through the catchment area. It is suggested that adsorption to, or co-precipitation with, such Fe-containing particles may have potential to be used as the initial step in a treatment method based on natural attenuation processes. Furthermore, the fraction of particulate bound metals decreased dramatically upon passing the lake Vormträsket, suggesting that some of these metals may be removed from the river system, at least temporally.     

Arsenic Mining Waste in the Catchment Area of the Madrid Detrital Aquifer (Spain)

In recent years, elevated arsenic concentrations in groundwater used for drinking water supplies have been recognised in the Madrid Tertiary detrital aquifer. Although only natural causes have been suggested as the source of arsenic, this study aims to highlight that the anthropogenic contribution cannot be disregarded. During the sub-catchment??s areas sampling, we found many geographical sites where natural arsenopyrite [FeAsS] originally encapsulated in pegmatite bodies and quartz veins, was artificially outcropped and dumped out, since mining wastes were scattered and exposed to weathering. Several mineral and ground specimens were collected to analyse its mineralogical and chemical composition by X-Ray Diffraction (XRD) and X-Ray Fluorescence (XRF) spectrometry and by Environmental Scanning Electron Microscope (ESEM). Both, the abundant existence of secondary phases, such as scorodite [FeAsO₄?2H₂O] and jarosite [KFe₃(SO₄)₂(OH)₆], much more soluble than arsenopyrite, and the lixiviation experiments of arsenopyrite in acidic media to simulate acid mine drainage (AMD) conditions, usually found in old mining districts, point to a potential risk of arsenic contamination of surface water bodies, which operate as recharged waters of the aquifer in the studied area. The elemental determination of heavy metals present in ground samples by XRF analyses, reaching up to 1,173 mg kg^?C1 of copper, 347 mg kg^?C1 of lead and 113,702 mg kg^?C1 of arsenic; and the physicochemical and arsenic fractionation studies of soil samples, led us to classify the soil as Spolic Technosol (Toxic). The contamination of the area due to old mining activities could release arsenic to Madrid water supplies; accordingly, additional decontamination studies should be performed.     

Elemental Uptake and Root-Leaves Transfer in Cistus Ladanifer L. Growing in a Contaminated Pyrite Mining Area (Aljustrel-Portugal)

Soils at the contaminated Aljustrel mining area situated in SWPortugal in the Iberian Pyrite Belt, and Cistusladanifer L., an autochthonal aromatic bush, were investigated to quantify the most relevant elements present in soils and in the plant, and to evaluate the possibility of phytoremediation of that area, particularly concerning the elements of higher pollutant potential.Multielemental (Mg, S, Cl, K, Ca, Cr, Mn, Fe, Cu, Zn, As, Br and Pb) characterisation of the soils and C. ladanifer leaves was carried out by Energy-Dispersive X-Ray Fluorescence spectrometry (EDXRF). Subsequently, due to their abundance in the soil and significant elevation compared to the control site, potential toxicity and/or biological significance, Mn, Cu, Zn, and Pb were determined by Atomic Absorption Spectrometry (AAS) in samples of soils, as well as in the roots and leaves of plants. C. ladanifer is able to survive and grow in soils having high concentrations of such toxic elements and to accumulate Mn.The bioavailability of Mn, Cu, Zn and Pb in the soils was evaluated by determining the contents of the elements in a solution of 0.5 M ammonium acetate, 0.5 M acetic acid and 0.02 M EDTA, pH 4.7, after soil extraction. Comparison of the values obtained with the corresponding element concentration in leaves give us a model of C. ladanifer's capacity to avoid these metals to reach toxic levels in the plant or their toxic effects when such levels are exceed, as in the case of Mn.     

Remediation of As-Contaminated Soils in the Guadiamar River Basin (SW, Spain)

In 1998, the pond containing the ore wastes from a pyrite mine in Aznalcóllar (SW, Spain) broke open, spilling some 36×10⁵ m³ of acidic waters and 9?×?10⁵ m³ of tailings containing high concentrations of As and heavy metals. The affected area was around 55 km² of predominantly agricultural soils. After the clean-up of the tailings, many remediation actions were undertaken and the use of blocking agents to immobilize the As was one of the most extended measure. The first experiment performed was to determine the most important soil components in As adsorption under acidic conditions. A second experiment was conducted to neutralize the acidity caused by the solution coming from the tailings undergoing oxidation; an adequate liming material (sugar-refinery scum) was selected and the application rates were established. After the remediation measures, the zone was monitored for three years. A detailed study in four experimental plots located in the most polluted sector was carried out to test the influence of iron oxides in the As immobilization. The use of red soils of the area (rich in free-iron oxides Fe_d) was established as an appropriate material in the remediation of the area.     

基于模型的上海郊区地下水氮素非点源污染特征研究

农业非点源污染是造成上海郊区地下水污染的主要因素,定量分析预测农业生产过程氮素的迁移转化规律是有效控制地下水污染的重要环节。以上海市浦东新区新场镇果园村的桃园为研究对象,借助生物地球化学过程模型（DNDC）和长期水文影响评价模型（L-THIA）,基于连续观测数据,详细分析了农业生产过程中氮素造成的非点源污染,特别是对周边地表、地下水的影响。结果表明,地表水总氮均值达6.34mg·L-1,远劣于地表水Ⅴ类标准（≤2.0mg·L-1）;地下水中总氮均值达16.85mg·L^-1,远劣于地表水Ⅴ类标准（≤2.0mg·L^-1）。约有20%采样点硝态氮含量属于地下水Ⅴ类（〉30mg·L^-1）。野外检测数据表明,该区地表水、地下水污染均严重超标,不宜饮用。模型分析显示,水体污染源主要来自桃园生产中施用的肥料,其中就模拟结果的数值可以得出,大约年农田氮输入量的1.7%通过土壤径流进入地表水,约3.5%经过土壤渗漏进入地下水,实测地下水中氮含量占桃园总氮输入量的5.8%。因此,合理调整施肥措施和施肥结构是减少土壤-水体中氮素污染的有效途径。     

Impact of Acid Mine Drainage (AMD) on Water Quality, Stream Sediments and Periphytic Diatom Communities in the Surrounding Streams of Aljustrel Mining Area (Portugal)

Aljustrel mining area is located in the Iberian Pyrite Belt, one of the greatest concentrations of massive sulphide deposits that extends from Lousal (Portugal) to Aznalcóllar (Spain). The surrounding streams, Roxo, Água Azeda and Água Forte, are influenced by the erosion of the tailing deposits and the input of acid mine drainage (AMD) from the abandoned Aljustrel pyrite mines, recently reopened in 2007. The purpose of this study was to understand how these adverse conditions influenced the stream sediments, water quality and periphytic diatom communities and establish the pre-restoration local conditions to judge the success of rehabilitation program now under way. For stream sediments, the highest metal concentration samples were found at sites F, G and H. Arsenic, Cu, Fe, Pb and Sb detected concentrations, generally exceeded the probable effect concentration values reaching level 4: the highest toxicity level. In surficial water samples of AMD affected sites (F, G and H), low pH values (1.5 to 3.5) and high metal concentrations of As (6,837 μg L^?1), Cd (455 μg L^?1), Cu (68,795 μg L^?1), Fe (1,262,000 μg L^?1), Mn (19,451 μg L^?1), Pb (136 μg L^?1), and Zn (264,377 μg L^?1) were found. In these sites, the diversity index (H′) for diatoms was low (0.6 to 2.8) and the dominant taxa were Eunotia exigua (site F, 33.5%) and Pinnularia acoricola (abundances in sites: F, 86.8%; G, 88.5%; and H, 91.1%). In opposition, in less AMD impacted, H′ was high (1.5 to 4.6) and low metal concentrations and high pH were found. Achnanthidium minutissimum was the dominant taxon in (abundances in sites: A, 76.1% and B, 24.39%). Canonical correspondence analysis showed that spatial variation due to mine influence was more important than seasonal variation, which did not show any pattern.     

Monitoring of Organic Compounds and Trace Metals During a Dredging Episode in the Göta Älv Estuary (SW Sweden) Using Caged Mussels

The concentrations of selected trace metals, organotins, polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs) were determined in caged blue mussels (Mytilus edulis) during dredging operations in the Göta Älv Estuary (SW Sweden). Maximum values of pollutants in mussel tissues were found after the dredging started. Our results showed that the dredging caused mobilization of organotins from the sediments to the water column during the experimental period. Multidimensional scaling (MDS) and cluster analysis were applied to compare and establish relationships between levels of pollutants in mussels and sampling sites during the experimental period. In order to evaluate the biological effects of contaminants, genotoxic damage was measured using the Comet assay, and its potential application for environmental monitoring is discussed.     

Determination of Toxicity of Spoil Substrates After Brown Coal Mining Using a Laboratory Reproduction Test with Enchytraeus crypticus (Oligochaeta)

Laboratory-reared cultures of Enchytraeus crypticus were used in a reproduction toxicity test to evaluate the toxicity of 46 spoil substrates collected in four brown coal mining areas in the Czech Republic and Germany. A set of substrate parameters (pH, conductivity, Na, Ca, K, Al, Fe, loss of ignition and polyphenol contents) were measured for each spoil and correlated with spoil toxicity for E. crypticus. Toxicity increased with decreasing pH and increasing Al, Fe content. Spoil with a pH below 3 did not support the survival of E. crypticus. However, some alkaline spoils with high conductivity and ion concentration were also toxic. Toxicity was positively correlated with the loss of ignition and polyphenol content. The results indicate that the toxicity of post-mining spoil substrates have multiple origins. Most frequently the toxicity of post-mining substrates corresponds with low pH and consequent toxicity of Al and Fe. However some substrates may be toxic due to high ion concentrations. The potential role of fossil organic matter (namely polyphenols) in toxicity of post-mining substrates requires further research.     

便携式X射线荧光光谱法(PXRF)在矿区农田土壤 重金属快速检测中的应用研究

针对我国普遍存在的土壤重金属污染问题,迫切需要开展土壤重金属的快速检测与评价方法研究。本文采用便携式X射线荧光光谱法(PXRF)和传统实验室方法对云南会泽铅锌矿区农田土壤As、Pb、Cu和Zn进行测定,分析了PXRF法的应用效果。结果表明:1PXRF法测定的精密度与准确度满足我国农田土壤环境质量检测技术规范中规定的仪器检测要求;2土壤As、Pb、Cu和Zn的PXRF法测定值与传统实验室测定值具有良好的一致性,Pb、Cu和Zn的决定性系数均大于0.70;3基于PXRF法原位测定、PXRF法异位测定和传统实验室测定结果的研究区土壤As、Pb、Cu和Zn具有相似的空间分布规律。可见,PXRF法可用于矿区周边农田土壤As、Pb、Cu和Zn的快速检测、污染筛查与评价。     

Arsenic and Heavy Metal Pollution of Soil,Water and Sediments in a Semi-Arid Climate Mining Area in Mexico

The environmental impact of arsenic and heavy metals on a 105 km² area of the historical and recent mining site of Villa de la Paz-Matehuala, San Luis Potosí (Mexico) was evaluated. Results of soil samples reported concentrations between 19–17 384 mg kg^-1 As, 15–7200 mg kg^-1 Cu, 31–3450 mg kg^-1 Pb and 26–6270 mg kg^-1 Zn, meanwhile, the concentrations in dry stream sediment samples were found to vary between 29–28 600 mg kg^-1 As, 50–2160 mg kg^-1 Pb, 71–2190 mg kg^-1 Cu, and 98–5940 mg kg^-1 Zn. The maximum arsenic concentration in pluvial water storage ponds (265 μg L^-1), near the main potential sources of pollution, exceed by 5 times the Mexican drinking water quality guideline (50 μg L^-1). The arsenic concentrations in water storage ponds and stream sediments decrease as distance from the potential sources increase. A special case is the `Cerrito Blanco' area located 5 km east of Matehuala, where the highest arsenic concentration in water was found (>5900 μg L^-1), exceeding by 100 times the established guideline, thus representing a severe health risk. The results suggest that arsenic and heavy metal dispersion from their pollution sources (historical and active tailings impoundments, waste rock dumps and historical slag piles), is mainly associated in this site with: (1) fluvial transportation of mine waste through streams that cross the area in W–E direction; and (2) aeolian transportation of mineral particles in SW–NE direction. Finally, control measures for pollution routes and remediation measures of the site are proposed.     

Iron absorption,localization, and biomineralization of Cynodon dactylon,a perennial grass from the Río Tinto basin (SW Iberian Peninsula)

Cynodon dactylon (L.) Pers. is a perennial rhizomatous grass (Poaceae), grown for cattle nutrition on the riverbanks of Río Tinto (Southwest Iberian Peninsula, Spain), a highly acidic area with high concentrations of iron (Fe) and other metals. This study focuses on the absorption, distribution, and accumulation of Fe in the root, rhizome, and leaves of C. dactylon under controlled conditions. Plants collected from Río Tinto were grown in a Hoagland solution containing 500 mg kg^–1 of ferrous Fe. Samples were collected up to 2 months after exposure and analyzed for total Fe concentration using inductively coupled plasma–mass spectrometry (ICP‐MS) and for Fe distribution and bioformations by scanning electron microscopy (SEM) with an energy‐dispersive x‐ray analyzer (EDX). The results show high concentrations of Fe in all plant organs, with fast Fe translocation from roots to leaves. Iron bioformations composed mainly of Fe, S, and K were detected in all plant organs and were especially apparent in roots and leaves. These results differ from those reported for another species of Poaceae, Imperata cylindrica, which grows under the same environmental conditions, suggesting the existence of different resistance strategies between species of the same family.     

Spatial Distribution and Temporal Trends of Polycyclic Aromatic Hydrocarbons (PAHs) in Sediments from Lake Maryut, Alexandria, Egypt

Surface and core sediments from Lake Maryut, Egypt, one of the most polluted lakes in Egypt, were analyzed for polycyclic aromatic hydrocarbons (PAHs) using gas chromatography?Cmass spectrometry. This investigation represents the first extensive study of the distribution and sources of PAHs in sediments from Lake Maryut. The total PAHs concentrations (sum of 39 PAH compounds) in surface sediments varied greatly depending on the sampling location and ranged from 106 to 57,800 ng/g dry weight with a mean concentration of 6,950 ng/g. The most polluted areas are distributed in areas which are mainly influenced by municipal sewage and industrial effluent discharges, suggesting a direct influence of these sources on the pollutant distribution patterns. PAH concentrations were one to two orders of magnitude higher in comparison with those reported for riverine/estuaries systems around the world. Molecular indices, such as pyrogenic index (PI), methylphenanthrenes to phenanthrene ratio, HMW_PAH/LMW_PAH, A-PAHs/P-PAHs, FL/FL?+?PY, BaP/BaP?+?C, IP/IP?+?BgP, and Per/??(penta-aromatics) were calculated to evaluate different hydrocarbon origins and their relative importance. In general, sediments from the main basin and northwest basin of Lake Maryut showed the highest PAH concentrations with petrogenic signatures, indicating major sources of petrogenic PAHs in the city. On the other hand, lower levels of PAHs with a pyrogenic signature were widely recorded in areas that are distant from anthropogenic sources. At other locations, both petrogenic and pyrogenic inputs were significant. The concentrations of perylene relative to the penta-aromatic isomers are dominant especially in locations associated with terrestrial inputs and in the deepest core sediments, indicating diagenetic origin for the presence of perylene. Temporal trends of PAH concentrations in both cores sediments were influenced by input pathways and followed the economic development and the environmental policies of the Egyptian Government in the last 15 years. Finally, PAH levels in sediments were compared with Sediments Quality Guidelines (effects range median?Ceffects range low) for evaluation probable toxic effects on organism. Results suggest an ecotoxicological risk for benthic organisms mainly in the main basin area, where high concentrations of PAHs were found in sediments influenced by anthropogenic activities.     

Inorganic Parameters as Water Quality Indicators in Acidic Groundwater in a Tropical Region – Brasilia-DF (Brazil)

In Brazilian Tropical Cerrado Region, reactions related to parental-material breakdown and oxisols genesis strongly affect the groundwater chemical characteristics. These reactions are responsible for the low water pH values, the soil charge balance, and the re-equilibrium of dissolved inorganic carbon species. Brasilia, the capital of Brazil, lies in the Distrito Federal, in the central part of the Brazilian Cerrado Region and has been experiencing an intense urban development during the last 15 years. Many town-house complexes have been built without proper water supply or wastewater disposal conditions. In this work, we discuss the adequacy of traditional ground waters geochemical classification models applied to the most exploited aquifers in DF. Forty groundwater samples were collected and pH, conductivity and total dissolved solids were determined in the field. Na, K, Ca, Mg, Fe, Al, Cu, Cd, Cr Mn e Zn were determined by Inductively Coupled Plasma Atomic Emission Spectrometry and Atomic Absorption Spectrophotometry. We identify inorganic indicators of human interference on the quality of these waters and also suggest a new mean of interpretation of dissolved inorganic elements based on statistic treatment of multivariate data. It is revealed a particular geochemical feature concerning to the alkali and the earth alkali metals concentrations, and a typical trace-element behaviour, closely related to the human activities and to the geological-bearing material characteristics. For all of the samples supposed to be altered by any kind of human activity, the physico-chemical parameters were lower than the standards established by the water quality legal system.