Mineralogical and geochemical signature of mine waste contamination, Tresillian River, Fal Estuary, Cornwall, UK

The mineralized district of SW England was one of the world's greatest mining areas, with mining commencing in the Bronze age, peaking in the 1850s to 1890s, but still continuing to the present day. Consequently, it is not surprising that mining has had a major impact on the environmental geochemistry of SW England. In this study, the mineralogical and geochemical signature of mine waste contamination within the Fal Estuary at Tresillian, Cornwall, has been examined. A pulse of mine waste contamination is recognized at approximately 50?cm below present day sediment surface. Sn, As, Cu, Pb, and Zn are all enriched within this contaminated interval with up to 1800 mg?kg^–1 Sn, 290 mg?kg^–1 As, 508 mg?kg^–1 Pb, 2210 mg?kg^–1 Zn, and 1380 mg?kg^–1 Cu. Within this interval, the dominant minerals present include chalcopyrite, arsenopyrite, pyrite, cassiterite, Fe–Ti oxides (ilmenite and ?rutile), wolframite, sphalerite, baryte, zircon, monazite, tourmaline and xenotime. In addition, man-made slag products commonly occur. The exact timing of the release of mine waste into the estuary is poorly constrained, but probably occurred during or immediately following the peak in mining activity in the nearby Camborne-Redruth district, which was between 1853 and 1893. The mine waste may have entered the estuary either via the Tresillian River and its tributaries or via Calenick Creek and the Truro River and/or the Carnon River which flows into Rostronguet Creek.     

The spatial distribution and source of arsenic, copper, tin and zinc within the surface sediments of the Fal Estuary, Cornwall, UK

ABSTRACT Estuarine sediments commonly form major sinks for contaminants released during industrial activity. Many industrial processes lead to the release of metals initially in solution, which can then be adsorbed on to, for example, Fe hydroxides or clay minerals. However, in the mining industry, there are two major contaminant waste streams: (1) metals discharged in solution via mine drainage; and (2) particulate grains of the ore‐forming or related minerals released after ore processing. The release of particulate waste can have a major long‐term impact on environmental geochemistry. In this study, we have mapped the distribution of arsenic, copper, tin and zinc within the surficial sediments of the Fal Estuary, Cornwall, UK, an area that drains a historically important polymetallic mining district. There are clear spatial variations in the contaminants, with the highest levels (> 2800 p.p.m. As, > 5000 p.p.m. Cu, > 3000 p.p.m. Sn and > 6000 p.p.m. Zn) within Restronguet Creek on the western side of the estuary. Mineralogical studies show that small (< 20 µm) grains of detrital arsenopyrite, chalcopyrite, cassiterite and sphalerite are very abundant within the surface sediments. Most of the sulphide grains are fractured, but mineralogically unaltered, although some grains show alteration rims caused by oxidation of the sulphides. The geochemistry and mineralogy are indicative of sediment supply from the discharge of particulate waste into the estuary during historical mining activity. Subsequently, this particulate waste has been largely physically and biologically reworked within the surface sediments. Although considerable effort has been made to minimize contaminants released via mine drainage into the estuary, the potential flux of contaminants present within the intertidal and subtidal sediments has not been addressed. Benthic invertebrates living within the area have adapted to be metal tolerant, and it is likely that the dominant source of bioavailable metals is a result of alteration of the particulate mine waste present within the intertidal and subtidal sediments.     

Mineralogy and heavy metal content in sediments from Rio Gato,Carelmapu and Cucao,Southern Chile

In southern Chile, with a mild and rainy climate, high levels of heavy metals have been detected in many gold placer deposits. Many of the contaminants pose risks to human life, and consequently damage the trofic chain in this environment. The study zones selected correspond to the handicraft gold-bearing sands of Rio Gato (Los Muermos), Carelmapu and Cucao. These are all located in the X Region of “Los Lagos” in Chile. The type of methodology used in the characterization of the associated mineralization consists of testing each representative sample with a grain size distribution, statistical parameter analysis and a mineralogical analysis, using a binocular magnifying glass, a petrographic microscope, XRD and SEM/EDX. The chemical composition was defined by means of X ray fluorescence and micro-chemical analysis. The results of the study about sediments in southern Chile are presented. The major concentrations of heavy minerals are generally located in areas of dynamic river energy. In the samples, more than 70% of the heavy minerals were distributed among grain sizes corresponding to thin sand with good grain selection (meshes of 0.25–0.06 mm). The main mineral phases present in the analysed samples were gold, zircon, olivine, ilmenite, hornblende, hypersthene, hematite, garnet, chromite, chlorite, augite, amphibolitic-epidote, etc. The main heavy metals found as a result of the study were mercury, lead, cadmium, chrome, tellurium, indium, zinc, cobalt, copper, platinum, gold, etc., and as well some less common elements like cerium, praseodymium, gadolinium, neodymium, samarium and lanthanum. This research work is only a starting point for carrying out a risk probability mapping of heavy metals and the mineralogy of the Cucao, Carelmapu and Rio Gato gold-bearing sands.     

Characterization of sediments in an abandoned mining area; a case study of Mansfeld region,Germany

The distribution of selected heavy metals, including some radionuclides, metalloids and non-metals was determined in stream sediments in a region influenced by abandoned copper mining and ore processing activities. A considerable amount of the ore processing waste with a very complex composition and highly elevated concentrations of zinc, sulfur, lead, copper, arsenic, and a lot of other elements in the range between 100 and 1,000 mg/kg (Sb, Mn, Ni, Cr, Cd, Hg, and Ag) was piled up on mine dumps. The dispersion of the pollutants originating from this source and their environmental impact were investigated. Both, sediments and original waste material were studied to indicate the pathways and the mobilization behavior of different pollutants. For this purpose, the process of the elution of pollutants by application of different fractionation schemes was studied. The capabilities of different analytical techniques are shown for the analysis of solid samples (X-ray fluorescence spectrometry, Gamma-spectrometry) and liquid ones (ICP-atomic emission spectrometry, ICP-mass spectrometry and different techniques of atomic absorption). Additionally, the coupling of ion chromatography and ICP-MS detection was used to study the distribution of arsenic species in the sediment cores of a lake which acts as a natural sink for the region.     

Georadiochemical evidence to weathering of mining residues of the Mansfeld mining district,Germany

Mining heaps are used as archives for the investigation of weathering processes. Aim of this work was to investigate the different weathering behavior of heap materials derived from Kupferschiefer mining with respect to environmental hazard. For this purpose, Kupferschiefer and slag material of two heaps of different age were examined regarding to the radionuclide distribution and geochemical composition. By measuring of the local dose rate, performing digital autoradiography and gamma spectrometry the radiological load of the heaps and the heap materials was determined. The geochemical characterization of the samples was performed by XRF, ICP–OES and ICP–MS. The results show a clear higher radionuclide load of the younger slag heap. A depletion of chalcophile and lithophile elements in the older slag was determined. Apart from a homogeneous radionuclide distribution, considerable radionuclide enrichments in fossil fragments could be proven. The results reveal a different weathering behavior of slag material in comparison to the Kupferschiefer depending on the chemical binding of the elements on organic and inorganic species. Natural organic matter as well as apatite in Kupferschiefer act as retention barrier for some metals.     

Heavy metal concentrations in shallow marine sediments affected by submarine tailings disposal and artisanal gold mining,Buyat-Ratototok district,North Sulawesi,Indonesia

Trace element concentrations in shallow marine sediments of the Buyat-Ratototok district of North Sulawesi, Indonesia, are affected by submarine disposal of industrial gold mine tailings and unregulated dumping of tailings and wastewater from small-scale gold mining using mercury amalgamation. Industrial mine tailings contained 590–690 ppm arsenic, 490–580 ppm antimony, and 0.8–5.8 ppm mercury. Tailings-affected sediment As and Sb concentrations were 20–30 times higher than in muddy sediments not contaminated with tailings, and 50–60 times higher than pre-mining average. Highest mercury concentrations were observed in sediments affected by small-scale mining using mercury amalgamation (5–29 ppm). Concentrations of most other trace elements were comparable in sediments affected by both types of mining and were slightly higher than regional averages for sediments collected before the onset of industrial mining. Elevated concentrations of both As and Sb in approximately equal proportions suggest tailings dispersal of at least 3.5 km. Mercury released from artisanal gold mining dispersed up to 4 km from river mouths. Slight increases in concentrations of non-mercury trace elements in areas affected by artisanal mining over pre-industrial mining concentrations were probably caused by increased rates of erosion. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Spatial variations in heavy metals on tidal flats in the Yangtze Estuary,China

Surface samples are used to determine onshore-offshore variations in heavy metal concentrations on tidal flats on Chongming and Hengsha Islands in the Yangtze Estuary, China. The Mann-Whitney U-Test suggests that proximity to the estuarine turbidity maximum does not result in significantly higher metal concentrations on tidal flats. Principal Components Analysis shows that grain-size is the primary control on metal concentrations, reflecting the occurrence of salt marsh and mud and sand flats. Sediment quality is comparable to that of pristine estuaries because of dilution by high river sediment loads.     

Geochemical investigations of slags from the historical smelting in Freiberg, Erzgebirge (Germany)

The Freiberg area in the Saxon Erzgebirge (Ore Mountains) represents one of the oldest mining districts in Germany. Argentiferous ore mineralizations with lead, zinc and copper are dominating in this region. Various waste products of mining can be found around Freiberg. In particular, the slags from ore smelting were and are regarded as unusable waste products. However, they preserve information on the smelting and weathering behaviour of slag, which makes them very useful sources of information for our purposes. To reconstruct the chemical processes during ore smelting, historical slag represents a most valuable archive. Therefore, the historical slag dump in Halsbach (Germany) was examined exemplarily for the Freiberg deposit. The slag was dumped approx. 400 years ago and is rich in lead. An interrelation between the slag and the metallurgical process applied can be made on the basis of chemical composition, appearance and microscopic results. The slags of the heap in Halsbach contain high concentrations of heavy metals (average contents in mg kg⁻¹: Zn 40,000; Pb 10,000; Cu 1500; U 1000). Enrichments of heavy metals in the organic-rich soil horizons within the range of the dump foot (maximum contents in the A-horizon in mg kg⁻¹: Zn 3719; Pb 9198; As 3017; Cu 963) imply a faint discharge of metals from the dump.     

The Oued Mellègue: Mining activity,stream sediments and dispersion of base metals in natural environments,North-western Tunisia

In the Northwest of Tunisia, mining works have occurred in an area of vital water reserves and resources (Oued Mellègue and Oued Mejerda), which represent nearly 81% of total potential of water in the region. Demographic growth, insufficient drinkable water, agriculture and industrial plants are factors responsible for the strong demand of this resource. Water supply is done by an interconnected battery of dams built on the major watercourses, the first of which, the Mellègue dam, was erected in the 1960s. Nowadays, most of the mines are closed for almost two decades although one is still active: (Jerissa for Fe). It is important to emphasise the fact that there are millions of cubic metres of abandoned tailings, mainly from Pb–Zn–Ba mines, which are not surveyed, representing a serious threat to the environment.     

Distribution and assessment of sediment toxicity in Tamaki Estuary,Auckland, New Zealand

Heavy metal levels in surface sediments from Tamaki Estuary demonstrate significant up estuary increases in Cu, Pb, Zn, Cd and mud concentrations. Increased metal levels towards the head of the estuary are linked to local catchment sources reflecting the historical development, industrialisation and urbanisation of catchment areas surrounding the upper estuary. The relatively narrow constriction in the middle estuary (Panmure area), makes it susceptible to accumulation of upper estuary pollutants, since the constriction reduces circulation and extends the time required for fine waterborne sediments in the upper estuary to exchange with fresh coastal water. As a result fine fraction sediments trapped in the upper estuary facilitate capture and retention of pollutants at the head of the estuary. The increase in sandy mud poor sediments towards the mouth of the estuary is associated with generally low metal concentrations. The estuary’s geomorphic shape with a mid estuary constriction, sediment texture and mineralogy and catchment history are significant factors in understanding the overall spatial distribution of contaminants in the estuary. Bulk concentration values for Cu, Pb, Zn, and Cd in all the studied surface samples occur below ANZECC ISQG-H toxicity values. Cd and Cu concentrations are also below the ISQG-L toxicity levels for these elements. However, Pb and Zn concentrations do exceed the ISQG-L values in some of the surface bulk samples in the upper estuary proximal to long established sources of catchment pollution.     

Sediment storage and severity of contamination in a shallow reservoir affected by historical lead and zinc mining

A combination of sediment-thickness measurement and bottom-sediment coring was used to investigate sediment storage and severity of contamination in Empire Lake (Kansas), a shallow reservoir affected by historical Pb and Zn mining. Cd, Pb, and Zn concentrations in the contaminated bottom sediment typically exceeded baseline concentrations by at least an order of magnitude. Moreover, the concentrations of Cd, Pb, and Zn typically far exceeded probable-effects guidelines, which represent the concentrations above which toxic biological effects usually or frequently occur. Despite a pre-1954 decrease in sediment concentrations likely related to the end of major mining activity upstream by about 1920, concentrations have remained relatively stable and persistently greater than the probable-effects guidelines for at least the last 50 years. Cesium-137 evidence from sediment cores indicated that most of the bottom sediment in the reservoir was deposited prior to 1954. Thus, the ability of the reservoir to store the contaminated sediment has declined over time. Because of the limited storage capacity, Empire Lake likely is a net source of contaminated sediment during high-inflow periods. The contaminated sediment that passes through, or originates from, Empire Lake will be deposited in downstream environments likely as far as Grand Lake O’ the Cherokees (Oklahoma).     

GIS-based colour composites and overlays to delineate heavy metal contamination zones in the shallow alluvial aquifers, Ankaleshwar industrial estate, south Gujarat, India

In an attempt to delineate heavy metal contamination precincts and to evaluate the extent and degree of toxic levels, besides their possible sources, 38 water samples from Ankaleshwar Industrial Estate, south Gujarat, India were analyzed. By clutching geochemical analyses and GIS-based colour composites areas depicting anomalously high concentration of heavy metals (Mo, Zn, Pb, Ni, Co, Cd, etc.) in the groundwater were revealed. The multicomponent overlays in grey-scale facilitated in identifying situates of heavy metal ‘hot spots’, and lateral protuberances of the contamination plume around defile stretch of the main stream Amla Khadi flowing through the area. The multiple pollution plumes emerging from other parts of the area further coincide with effluent laden streams and small channels indicating industrial establishments as major sources of groundwater contamination. Influent nature of the streams, accelerated infiltration process, high mass influx and shallow groundwater table are the factors conducive for easy access of heavy metals to the phreatic aquifers affecting over 20 km² area. On the basis of P/U ratios (concentration of metals in polluted water to unpolluted water), geogenic and anthropogenic sources have been identified. Very high levels of technogenic elements present in the ground water raise concerns about possible migration into food crops, as the area is an important horticultural locale and is highly cultivated.     

Geochemical fractionation of heavy metals in Chilka Lake (east coast of India)—a tropical coastal lagoon

Chilka lake, the largest coastal lagoon of Asia is one of the most dynamic ecosystems along the Indian coast. Historically the lagoon has undergone a considerable reduction in surface area due, in part, to input from natural processes but mostly due to human activities. The purpose of this investigation is to document the heavy metals' affinity for specific geochemical phases in the recently deposited sediments in the lagoon. Thirty-three samples were collected and analyzed for different geochemical phases of Fe, Mn, Cu, Cr, Ni, Pb, and Zn utilizing a sequential extraction scheme. In the nonlithogenous fraction, the exchangeable fraction was not geochemically significant, having <2% of the total metal concentration for all the elements. However, the carbonate fraction contained the following percentages of the total concentration: <1% Fe, 13% Mn, 6% Cu, 4% Cr, 8% Ni, 13% Pb, and 12% Zn, suggesting the detrital origin of the sediments. Reducible and organic matter-bound fractions were the significant phases in the nonlithogenous fraction, containing 9% Fe, 16% Mn, 15% Cu, 16% Cr, 16% Ni, 14% Pb, and 14% Zn in the former and 4% Fe, 3% Mn, 17% Cu, 3% Cr, 14% Ni, 15% Pb, and 14% Zn in the latter. The phenomenon has been attributed to the scavenging affinity of Fe-Mn oxides and affinity for sorption into organic matter of the lagoon sediments. The lithogenous, residual fraction generally considered as a guide for natural background values was determined to contain 87% Fe, 67% Mn, 61% Cu, 77% Cr, 61.3% Ni, 56% Pb, and 60% Zn of the total concentrations.     

Heavy metals on tidal flats in the Yangtze Estuary, China

 Five short cores were used to examine heavy metals on tidal flats in the Yangtze Estuary, China. Statistically insignificant trends in lead-210 and most metals with core depth are primarily due to high sedimentation rates. Metal contents are correlated with percent aluminum, which reflects the clay contents in the sediment, and they are also affected by proximity to sewage outlets and local industry. National standards for copper are exceeded in four cores, zinc in one core, and arsenic in all cores. Heavy metal contents are generally lower on the Yangtze tidal flats compared to most other estuaries because high sediment loads dilute metal inputs. Received: 1 June 1999 · Accepted: 15 August 2000     

Evolution of heavy-metal profiles in river Weser Estuary sediments,Germany

Studies of heavy metal concentrations in porewaters and in sediments from the Weser Estuary, Germany, indicate that the depth distribution of Mn, Cd, and Cu in the solid phase is predominantly influenced by the subsurface redox regime, while Ni shows only moderate alteration. Based on solid-phase heavy metal data from eight locations in the study area, linear regressions of Fe, Mn, Cu, Ni, and Cd on Al allowed differences between the initial metal concentration and the concentration preserved in the sediments to be predicted. We calculate that, due to early diagenetic processes, Mn is enriched to 145 percent, while Cu and Cd are depleted to 71 percent and 46 percent, respectively, of the initial metal concentration in the near-surface sediment. Maximum depletion of Cd (84 percent), Cu (68 percent), Mn (54 percent), and Ni (24 percent) concentrations in the sediment, observed at a restricted area downcore, indicate the importance of post-depositional processes to metal preservation in the sediment. Without knowledge of the quantitative effects of diagenetic reactions on the preservation of metal concentrations in sediments, the depth distribution of metals in sediment cores may be misinterpreted as the effect of human activities.     

The distribution of heavy metals in an abandoned mining area; a case study of Strauss Pit, the Drake mining area, Australia: implications for the environmental management of mine sites

Surface water samples from the Drake mining area show elevated metal concentrations, notably cadmium, iron and zinc. A detailed study of a sphalerite /quartz vein from Strauss Pit and chalcopyrite and pyrite from the Adeline mine and Strauss Pit indicate that micro-scale analyses of ores are necessary for environmental management of mine sites. Analyses show that Cd is elevated, up to 2.1 % by weight, and is associated with sphalerite, replacing Zn, or to a lesser extent replacing Pb within small galena grains. High concentrations of Cu are also associated with the Strauss Pit ore as small chalcopyrite grains along the margins of the sphalerite vein, within the central quartz zone of the vein system, and as replacement rims on sphalerite grains. Chalcopyrite from the Adeline mine area, is by comparison, metal poor, but still contains elevated heavy metal concentrations. Whereas, pyrite and chalcopyrite, from Strauss Pit have variable heavy metal concentrations, with chalcopyrite from within sphalerite veins having higher Cd and Zn concentrations than chalcopyrite distal to the veins. Cadmium and other heavy metals within the ores are mobilised during sulphide weathering and enter the drainage network; precipitation of secondary oxidation minerals act as temporary stores for many heavy metals. The complexity of the mineral and heavy metal associations at Strauss Pit suggest that a detailed knowledge of these associations and distributions within ore bodies, and associated waste rocks, are needed by environmental managers of mine sites because the presence of havy metals may greatly affect the decision making process, and management strategies employed. Received; 14 July 1999 · Accepted: 17 August 1999     

Heavy metals in sediments of the Tecate River, Mexico

Ten sites along the Tecate River, Mexico were sampled to evaluate the cadmium, lead, nickel and chromium concentrations in sediments. The result shows contamination for cadmium in most of the sites, where two sites were class 4 (polluted to strongly polluted) according to geoaccumulation index proposed by Muller. Two sites were found polluted for all the heavy metals analyzed (Cr, Cd, Pb and Ni), indicating the effect of anthropogenic activities. A correlation between Ni and Cd concentration had been found indicating a common source. These metals are usually used in electroplating industry. The results of this study can be used for decision makers to prioritize measures to control the pollution for these metals.     

Bioaccumulation of heavy metals in oyster (Crassostrea virginica) tissue and shell

Oysters and sediment have been collected from most major US Gulf of Mexico bays and estuaries each year since 1986. Selected samples of oyster soft tissue, shell and sediments were analyzed for Cd, Cr, Cu, Fe, Mn, Pb, and Zn for this study. Concentrations varied considerably from place to place but ratios of metals remained relatively constant. Cu and Zn are greatly enriched in oyster tissues, which is related to their physiological function. Cd is enriched in oyster shell because of the easy substitution between Cd and Ca. The concentrations of Pb and Cr in oysters are significantly lower than that in sediment, suggesting a good discrimination against these metals by oysters. Metal variations are a result of both nature and human activity. Received: 13 September 1999 · Accepted: 8 December 1999     

Effects of historical mining activities on surface water and groundwater - an example from northwest Arizona

 The focus of this research was to determine the impact of abandoned mines on surface water and groundwater in the historical mining districts of the Cerbat Mountains, Arizona. The surface water in the mining areas was found to be contaminated by various combinations and concentrations of heavy metals. Elevated arsenic, cadmium, and iron concentrations were detected in most surface-water samples, while lead, copper, and zinc contamination differed from region to region, depending on the ore mined. The groundwater was seriously polluted by arsenic, cadmium, lead, zinc, iron, and manganese in the immediate vicinity of mines that processed ore on the site, such as the Tennessee Mine near Chloride. Chloride's groundwater, however, showed no evidence of contamination. Three possible explanations are discussed: immobilization of the heavy metals in the soil by chemical reactions and adsorption, dilution effects due to the rainy season in spring, or the existence of different groundwater systems. Received: 17 September 1996 · Accepted: 14 May 1997     

Heavy metals in freshly deposited sediments of the Gomati River (a tributary of the Ganga River): effects of human activities

 The concentrations of various metals (Cr, Cu, Co, Fe, Mn, Ni, Pb, Zn, and Cd) were determined in recently deposited surface sediments of the Gomati River in the Lucknow urban area. Markedly elevated concentrations (milligrams per kilogram) of some of the metals, Cd (0.26–3.62), Cu (33–147), Ni (45–86), Pb (25–77), and Zn (90–389) were observed. Profiles of these metals across the Lucknow urban stretch show a progressive downstream increase due to additions from 4 major drainage networks discharging the urban effluents into the river. The degree of metal contamination is compared with the local background and global standards. The geoaccumulation index order for the river sediments is Cd>Zn>Cu>Cr>Pb. Significant correlations were observed between Cr and Zn, Cr and Cu, Cu and Zn and total sediment carbon with Cr and Zn. This study reveals that the urbanization process is associated with higher concentrations of heavy metals such as Cd, Cu, Cr, Pb, and Zn in the Gomati River sediments. To keep the river clean for the future, it is strongly recommended that urban effluents should not be overlooked before their discharge into the river. Received: 16 February 1996 · Accepted: 29 February 1996