Mobilization and attenuation of heavy metals within a nickel mine tailings impoundment near Sudbury, Ontario, Canada

 The oxidation and the subsequent dissolution of sulfide minerals within the Copper Cliff tailings area have led to the release of heavy metals such as Fe, Ni, and Co to the tailings pore water. Dissolved concentrations in excess of 10 g/l Fe and 2.2 g/l Ni have been detected within the shallow pore water of the tailings, with increasing depth these concentrations decrease to or near analytical detection limits. Geochemical modelling of the pore-water chemistry suggests that pH-buffering reactions are occurring within the shallow oxidized zones, and that secondary phases are precipitating at or near the underlying hardpan and transition zones. Mineralogical study of the tailings confirmed the presence of goethite, jarosite, gypsum, native sulfur, and a vermiculite-type clay mineral. Goethite, jarosite, and native sulfur form alteration rims and pseudo-morphs of the sulfide minerals. Interstitial cements, composed of goethite, jarosite, and gypsum, locally bind the tailings particles, forming hardpan layers. Microprobe analyses of the goethite indicate that it contains up to 0.6 weight % Ni, suggesting that the goethite is a repository for Ni. Other sinks detected for heavy metals include jarosite and a vemiculite-type clay mineral which locally contains up to 1.6 weight % Ni. To estimate the mass and distribution of heavy metals associated with the secondary phases within the shallow tailings, a series of chemical extractions was completed. The experimental design permitted four fractions of the tailings to be evaluated independently. These four fractions consisted of a water-soluble, an acid-leachable, and a reducible fraction, as well as the whole-rock total. Twenty-five percent of the total mass of heavy metals was removed in the acid-leaching experiments, and 100% of the same components were removed in the reduction experiments. The data suggest that precipitation/coprecipitation reactions are providing an effective sink for most of the heavy metals released by sulfide mineral oxidation. In light of these results, potential decommissioning strategies should be evaluated with the recognition that changing the geochemical conditions may alter the stability of the secondary phases within the shallow tailings. Received: 9 April 1997 · Accepted: 21 July 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     

Distribution and sources of phosphorus in tidal river sediments in the Washington, DC, Area

 Sediments in the rivers and basins around Washington, DC, have high concentrations of phosphorus, which, based on geographic distributions, is largely derived from urban runoff and municipal sewage. Dissolved-particulate phosphate exchange reactions and biological uptake of dissolved phosphorus from the water column may be an added source of phosphorus to the sediments. Concentrations of total sedimentary phosphorus ranged from 24 to 56 μm P/g-dw, and were highest in areas near combined sewer outfalls. As a part of this study, sedimentary phosphorus was fractionated into Fe-P, Ca-P, Al-P, and organic phases using a selective-sequential leaching procedure. The distribution of the phases in all sediments analyzed follow the order , Fe-P>Ca-P>Al-P. Spatial variations in the amounts of phosphorus in the different phases is related to the sources of phosphorus to the area. The proportions of occluded Al-P and organic P are 10–20% of the total P, respectively. This suggests that phosphorus from natural sources is small compared to anthropogenic inputs in this area. The high leachable Fe-P and Ca-P in these sediments might contribute a substantial amount of P to the water column under conditions of remobilization. Received: 20 February 1996 · Accepted: 2 April 1996     

Geochemical factors controlling the chemical nature of water and sediments in the Gomti River, India

 R-mode factor analysis of the recently acquired data on water and sediment chemistry has been performed. Basic chemical parameters have been merged together which aid in interpreting a few empirical geochemical factors controlling the chemical nature of water and sediments of the Gomti River, a major Himalayan tributary of the Ganges drainage basin. Water chemistry seems to be controlled by three factors: bicarbonate, rainfall and silicate and phosphate factors. Sediment chemistry is largely controlled by the following four factors: clay, adsorption/desorption, Fe-Mn hydroxide and mercury factors. These factors show spatial and temporal variability in terms of their R-scores. Received: 8 September 1997 · Accepted: 15 December 1997     

Heavy metals in sediments of a large, turbid tropical lake affected by anthropogenic discharges

 Bottom-water data and trace metal concentration of Cu, Cr, Ni, Pb, Co, Zn, and organic matter in surficial sediment samples from 13 sampling stations of Lake Chapala in Mexico were studied. The lake is turbid with a great amount of flocculated sediments as a result of wind mixing, sediment re-suspension, and Lerma River discharges. Al distribution pattern in sediments was used as an indicator of the Lerma River discharges into Lake Chapala. The highest values of Cu (33.27 ppm), Cr (81.94 ppm), Pb (99.8 ppm), and Zn (149.7 ppm) were detected in sediments near the lake outlet. The bioavailable metal fraction is low for all metals except Pb, which shows 65–93% of the total metal concentration in bioavailable form. The minimum energy zone in the lake was related to organic matter concentration and was located in the SE part of the lake. An analysis of the studied parameters shows two zones: eastern zone (fluvio-deltaic) and central-western zone (lacustrine). Received: 9 September 1998 · Accepted: 16 November 1998     

Assessment of natural attenuation of aromatic hydrocarbons in groundwater near a former manufactured-gas plant, South Carolina, USA

 Shallow, anaerobic groundwater near a former manufactured-gas plant (MGP) in Charleston, South Carolina, USA, contains mono- and polycyclic aromatic hydrocarbons (MAHs and PAHs, respectively). Between 1994 and 1997, a combination of field, laboratory, and numerical-flow and transport-model investigations were made to assess natural attenuation processes affecting MAH and PAH distributions. This assessment included determination of adsorption coefficients (K _ad ) and first-order biodegradation rate constants (K _bio ) using aquifer material from the MGP site and adjacent properties. Naphthalene adsorption (K _ad =1.35×10^–7 m³/mg) to aquifer sediments was higher than toluene adsorption (K _ad =9.34×10^–10 m³/mg), suggesting preferential toluene transport relative to naphthalene. However, toluene and benzene distributions measured in January 1994 were smaller than the naphthalene distribution. This scenario can be explained, in part, by the differences between biodegradation rates of the compounds. Aerobic first-order rate constants of ¹⁴C-toluene, ¹⁴C-benzene, and ¹⁴C-naphthalene degradation were similar (–0.84, –0.03, and 0.88 day^–1, respectively), but anaerobic rate constants were higher for toluene and benzene (–0.002 and –0.00014 day^–1, respectively) than for naphthalene (–0.000046 day^–1). Both areal and cross-sectional numerical simulations were used to test the hypothesis suggested by these rate differences that MAH compounds will be contained relative to PAHs. Predictive simulations indicated that the distributions of toluene and benzene reach steady-state conditions before groundwater flow lines discharge to an adjacent surface-water body, but do discharge low concentrations of naphthalene. Numerical predictions were "audited" by measuring concentrations of naphthalene, toluene, and benzene at the site in early 1997. Measured naphthalene and toluene concentrations were substantially reduced and the areal extent of contamination smaller than was both observed in January 1994 and predicted for 1997. Measured 1997 benzene concentrations and distribution were shown to be relatively unchanged from those measured in 1994, and similar to predictions for 1997. Received: 26 June 1997 · Accepted: 25 August 1997     

Natural and anthropogenic influences on the geochemistry of Quaternary lake sediments from Holzmaar, Germany

 The accumulation of heavy metals and trace elements has been investigated in a well laminated sequence of Holocene and late Pleistocene lake sediments composed of diatomaceous gyttja, tuff and silt and clay sediments. Varve chronology of the annually deposited gyttja yielded a continuous high-resolution time sequence and allowed the absolute age dating of the sediment. Fluxes of elements remained largely uniform from the late Pleistocene into the Holocene (12 867–2 364 VT years ago; VT: varve time, years before 1950). Higher trace element and heavy metal fluxes occur from 2 322 to 862 VT years ago and reached their maxima in the uppermost sediments (<845 VT years ago). These increasing element fluxes correlate with increasing inputs of clastic material. The changing accumulation rates are the result of elevated soil erosion in the lake catchment caused by human settlement, deforestation and agricultural activities. Thus disturbances of the natural geochemical cycles of the Holzmaar region have occurred since the beginning of the Iron Age and especially since the beginning of the Middle Ages. Received: 29 May 1996 · Accepted: 19 August 1996     

Acid leached analyses of stormdrain and harbor sediments, New Zealand

 Sediments from stormdrain catchments in Wellington city and sediment traps from Wellington Harbor were sampled for trace metal content. Samples were analyzed for acid leached metal content by extraction with 0.11 mol acetic acid l^–1 and using ICP-MS. Cu and Zn levels in harbor sediment traps increased towards the periphery of the harbor, while Pb levels adjacent to a road almost doubled. In general, areas of light industry in the Inner City stormdrain catchments exhibited higher acid leached metal concentrations. However, large-scale renovation work probably contributed to point sources of high metal levels. The proximity of stormdrain outlets to recreational activities, such as wharf fishing and shellfish gathering, should be of prime concern to local authorities. Some positive correlations are found between acid leached and total metal levels. These may prove useful for assessing the biological impact of significant increases in total metal concentrations in the vicinity of Wellington Harbor. Significant savings in the time and costs of analyses may be achieved. Received: 27 February 1998 · Accepted: 27 April 1998     

A contemporary contamination record of stormdrain and harbour sediments, Wellington, New Zealand

 Sediments from stormdrain catchments and outlets in Wellington city and sediment traps from Wellington Harbour were sampled for trace metal content. Samples were analysed for total metal content using XRF and ICP-MS. High values of Pb and Zn were found in stormdrain catchments and outlets, decreasing to elevated background rock levels in the harbour. Maximum values were recorded in an inner city stormdrain catchment, with levels of Pb (4605 ppm), Cu (2981 ppm) and Zn (3572 ppm) all higher than the biological probable effects levels (PEL). Concentrations of As, Cr, Cu, Pb, Ni and Zn concentrations in all harbour sediment trap samples were below the PEL. The mean values for each harbour sediment trap sample can be used as an accurate historical baseline in future studies. Stormdrain samples with high trace metal levels were close to industrial and construction sites. The proximity of these outlets to recreational areas should be of concern to local authorities. Received: 28 August 1997 · Accepted: 15 December 1997     

Trace metal concentrations in lake and overbank sediments in southern Norway

 As, Be, Cd, Co, Cr, Cu, Hg, Ni, Pb, V, Se and Zn concentrations were determined and compared in lake and overbank sediments from 33 catchments without local pollution sources in southern Norway. There were no significant differences in concentrations of Be, Co, Cr, Cu, Ni, and V in overbank and pre-industrial lake sediments. In areas with shallow overburden, and significant influence from long-range atmospheric pollution, concentrations of As, Cd, Hg, Pb, Se, and Zn in overbank sediments were probably modified by vertical percolating water. In such areas, we suggest using lake sediments as a better sampling medium for mapping pre-industrial concentrations. Pre-industrial lake sediments yield natural concentrations of Hg and Se, which consist of both geogenic and natural atmospheric deposition. Important covariables like organic carbon content, Fe oxides, and fine mineral fraction were generally higher in pre-industrial lake sediments as compared to overbank sediments. By adjusting for such differences overbank sediments could be used as an alternative in mapping background concentrations of trace metals in regions with few lakes. Received: 19 February 1999 · Accepted: 17 April 1999     

Spatial distribution of major and trace elements in shallow reservoir sediments: an example from Lake Waco, Texas

 Sediment geochemistry of a shallow (6-m average) reservoir (Lake Waco) was evaluated for the spatial distribution of major and trace elements. Sixty bottom and core samples along a 21-km transect within the reservoir, 18 overbank sediment samples, and 8 rock types in the drainage area were collected and analyzed for major (Al, Ca, Fe) and trace elements (As, Ba, Cr, Cu, Hg, Mn, Ni, Pb, Sr, V, Zn). Elemental concentrations in the reservoir sediments closely correspond to concentrations in the regional rocks and represent a mixture of overbank sediment composition of the tributaries. Elemental concentrations were statistically regressed against Al concentrations in order to establish regional baseline levels and thereby distinguish natural from anthropogenic sources. Spatial geochemical trends, considered in terms of element-to-Al ratio versus V-to-Al ratio, relate to the natural and anthropogenic sources contributing to the elemental concentrations. The spatial elemental distribution in the reservoir, which receive sediments from two mineralogically contrasting basins, reflect textural and mineralogical transition within the reservoir and suggest a progressive mixing of sediment from the tributaries. The spatial elemental distribution and sediment texture suggest that the sediment-source, which determines the sediment-type, has a greater influence on the major- and trace-element distributions in shallow reservoir sediments than bathymetry. Received: 25 September 1997 · Accepted: 3 February 1998     

Total mercury and methylmercury in sediments near offshore drilling sites in the Gulf of Mexico

Concentrations of total Hg in sediments near six drilling sites in the Gulf of Mexico were elevated well above average background values of 40–80 ng/g. The excess Hg was associated with barite from discharged drilling mud. In contrast with total Hg, concentrations of methylmercury (MeHg) in these sediments did not vary significantly at nearfield (<100 m) versus farfield (>3 km) distances from the drilling sites. Observed variability in concentrations of MeHg were related to local differences in redox state in the top 10 cm of sediment. Low to non-detectable concentrations of MeHg were found in nearfield sediments that were anoxic, highly reducing and contained abundant H₂S. At most drilling sites, nearfield samples with high concentrations of total Hg (>200 ng/g) had similar or lower amounts of MeHg than found at background (farfield) stations. Higher values of MeHg were found in a few nearfield sediments at one site where concentrations of TOC were higher and where sediments were anoxic and moderately reducing. Overall, results from this study support the conclusion that elevated concentrations of MeHg in sediments around drilling sites are not a common phenomenon in the Gulf of Mexico.     

Coherent slumping of early postglacial lake sediments at Hall Lake, Ontario, Canada

Cores of organic postglacial sediment from Hall Lake, southern Ontario, Canada, are described. The laminated, calcareous sediments deposited between 9,000 and 8,000 B.P. have coherently slumped into the deep part of the lake, causing overturning and replication of parts of the sequence. This process may be considered as a mechanism for sediment focusing, since it involves reworking of marginal sediments into deeper areas. Unlike previously described mechanisms, it may be a source of error in the interpretation of diagrams of pollen percentages as well as accumulation rates. The slumping has only been recognized through the distortion of the laminae. It might not be possible to recognize slumping in unstratified sequences.     

Estimation of regionalized phenomena by geostatistical methods: lake acidity on the Canadian Shield

 This paper describes a geostatistical technique based on conditional simulations to assess confidence intervals of local estimates of lake pH values on the Canadian Shield. This geostatistical approach has been developed to deal with the estimation of phenomena with a spatial autocorrelation structure among observations. It uses the autocorrelation structure to derive minimum-variance unbiased estimates for points that have not been measured, or to estimate average values for new surfaces. A survey for lake water chemistry has been conducted by the Ministère de l'Environnement du Québec between 1986 and 1990, to assess surface water quality and delineate the areas affected by acid precipitation on the southern Canadian Shield in Québec. The spatial structure of lake pH was modeled using two nested spherical variogram models, with ranges of 20 km and 250 km, accounting respectively for 20% and 55% of the spatial variation, plus a random component accounting for 25%. The pH data have been used to construct a number of geostatistical simulations that produce plausible realizations of a given random function model, while 'honoring' the experimental values (i.e., the real data points are among the simulated data), and that correspond to the same underlying variogram model. Post-processing of a large number of these simulations, that are equally likely to occur, enables the estimation of mean pH values, the proportion of affected lakes (lakes with pH≤5.5), and the potential error of these parameters within small regions (100 km×100 km). The method provides a procedure to establish whether acid rain control programs will succeed in reducing acidity in surface waters, allowing one to consider small areas with particular physiographic features rather than large drainage basins with several sources of heterogeneity. This judgment on the reduction of surface water acidity will be possible only if the amount of uncertainty in the estimation of mean pH is properly quantified. Received: 3 March 1997 · Accepted: 16 November 1998     

Anthropogenic influences on hydrocarbon contents of sediments deposited in eastern Lake Ontario since 1800

 The amounts and types of extractable hydrocarbon components in sediment cores from the Rochester Basin of eastern Lake Ontario provide a record of environmental changes that have accompanied the settlement and population growth of the surrounding land areas. Sediments deposited prior to the mid-1800s contain low concentrations of hydrocarbons that are dominated by land-plant wax components. Concentrations begin to rise in the late 1800s as erosion of soil and nutrients from watershed areas accelerated. This pattern continues into modern times. Episodes of enhanced aquatic productivity are sometimes recorded in twentieth-century sediments by the dominance of algal hydrocarbons, but land-plant components typically predominate. Petroleum residues begin to appear in sediments deposited in the late 1800's but remain minor constituents of the hydrocarbon contents of modern sediments in the Rochester Basin. Received: 21 March 1995 · Accepted: 11 August 1995     

Heavy metal pollution in freshly deposited sediments of the Yamuna River (the Ganges River tributary): a case study from Delhi and Agra urban centres, India

 The Yamuna River sediments, collected from Delhi and Agra urban centres, were analysed for concentration and distribution of nine heavy metals by means of atomic adsorption spectrometry. Total metal contents varied in the following ranges (in mg/kg): Cr (157–817), Mn (515–1015), Fe (28,700–45,300), Co(11.7–28.4), Ni (40–538), Cu (40–1204), Zn (107–1974), Pb (22–856) and Cd (0.50–114.8). The degree of metal enrichment was compared with the average shale concentration and shows exceptionally high values for Cr, Ni, Cu, Zn, Pb and Cd in both urban centres. In the total heavy metal concentration, anthropogenic input contains 70% Cr, 74% Cu, 59% Zn, 46% Pb, 90% Cd in Delhi and 61% Cr, 23% Ni, 71% Cu, 72% Zn, 63% Pb, 94% Cd in Agra. A significant correlation was observed between increasing Cr, Ni, Zn, and Cu concentrations with increasing total sediment carbon and total sediment sulfur content. Based on the Müller's geoaccumulation index, the quality of the river sediments can be regarded as being moderately polluted to very highly polluted with Cr, Ni, Cu, Zn, Pb and Cd in the Delhi and Agra urban centres. The present sediment analysis, therefore, plays an important role in environmental measures for the Yamuna River and the planning of these city centres. Received: 21 June 1999 · Accepted: 1 October 1999     

Geochemical and mineralogical properties of sulfide-bearing fine-grained sediments in Finland

 The geochemical and mineralogical characteristics of bulk samples and various size fractions of sulfide-bearing fine-grained sediments in the Petalax area, western Finland, were studied with ICP-AES (aqua regia digestion and "total" digestion) and X-ray diffraction. The sediments, which are dominated by particles <0.06 mm (clay and silt size), are composed of phyllosilicates (micas, kaolinite, chlorite, vermiculite), quartz, feldspars, amphiboles, organic matter, and secondary S minerals. The chemical analyses show that Na, Ca, and Sr are enriched in the silt and sand fractions, that Zr is enriched in the silt fraction, and that the concentrations of all other studied metals (Al, Ba, Co, Cr, Cu, Fe, K, La, Mg, Mn, Nb, Ni, Sc, Th, Ti, V, Y, and Zn) increase from the sand to the clay fraction. Sodium, Ca, and Sr occur largely in poorly dissolved feldspars, which explains the distribution of these metals in the sediments. The increase in the concentrations of most metals in the clay fraction is interpreted to be the result mainly of an increase in phyllosilicates in this size fraction. A geochemical comparison between the sulfide-bearing fine-grained sediments and glacial till shows that the former are enriched in several potentially toxic metals. It is therefore argued that the hydrological and ecological problems associated with the sulfide-bearing sediments are related not only to the production of acidity in oxidized layers, but also to mobilization and dispersion of toxic metals. Strategies to minimize damage of freshwater systems in areas covered with sulfide-bearing fine-grained sediments are suggested. Received: 20 February 1997 · Accepted: 25 August 1997     

The role of geomorphic processes in the transport and fate of mercury in the Carson River basin, west-central Nevada

 The historic processing of precious metal ores mined from the Comstock Lode of west-central Nevada resulted in the release of substantial, but unquantified amounts of mercury-contaminated mill tailings to the Carson River basin. Geomorphic and stratigraphic studies indicate that the introduction of these waste materials led to a period of valley-floor aggradation that was accompanied by lateral channel instability. The combined result of these geomorphic responses was the storage of large volumes of mercury-enriched sediment within a complexly structured alluvial sequence located along the Carson River valley. Much of the contaminated sediment is associated with filled paleochannels produced by the cutoff and abandonment of meander loops, and their subsequent infilling with contaminated particles. Geochemically, these deposits are characterized by variations in mercury levels that exceed three orders of magnitude. Continued lateral instability, coupled with an episode of channel-bed incision, followed the decline of Comstock mining, and has reexposed contaminated debris within the banks of the river. Erosion of bank sediments reintroduces mercury-enriched particles to the modern channel bed. It is suggested on the basis of geochemical and sedimentological data that during the bank erosion process, much of the mercury associated with fine (<63 μ) valley-fill deposits are carried downstream without being incorporated to any appreciable extent within the channel-bed sediments. In contrast, mercury associated with larger and denser particles, particularly mercury-gold-silver amalgam grains, are accumulated in the channel-bed sediments as the river traverses polluted reaches of the Carson River valley. Concentration patterns developed along the modern channel indicate that the valley fill is the primary source of mercury to the river today. Thus, these data imply that efforts to reduce the influx of mercury to the aquatic environment should examine methods for reducing bank erosion rates. Received: 13 December 1996 · Accepted: 15 April 1997     

Assessment of mercury contamination and human exposure associated with coastal disposal of waste from a cinnabar mining operation, Palawan, Philippines

 An integrated geochemical and toxicological assessment of environmental mercury contamination and attendant human exposure in Honda Bay, Palawan was undertaken in 1995 following a nationally reported pollution scare centered on a coastal jetty, Sitio Honda Bay, constructed using approximately 1 million tons of tailings and beneficiation waste from a cinnabar mine. Mercury (Hg) data for marine and fluvial sediments, fish tissues and human hair indicate that the toxicological hazard is considerably lower than initially reported by state environment and health officials. Typical Hg concentrations in surficial Honda Bay sediments were found to lie within the global background range (<60 μg/kg). Downcore profiles provide no evidence of enhanced Hg fluxes coincident with the onset of mining and/or coastal tailings disposal. The mean and median Hg concentrations recorded in tissues of six species of Honda Bay fish are compliant with thresholds established by the US Environmental Protection Agency (US-EPA) for marketable stocks. Earlier reports of 'Minamata range' Hg concentrations in fish and shellfish from Honda Bay remain unsubstantiated. Geochemical analyses of samples of the Sitio Honda Bay substrate have confirmed the prevalence of solid-phase Hg concentrations to ca. 340 mg/kg. The speciation of Hg is, however, dominated by secondary oxides of low bioavailability. The mean Hg concentration in hair from Sitio Honda Bay residents (4.41 mg/kg) was found to be statistically analogous to that for a neighbouring coastal community unimpacted by the coastal disposal of mine waste. A negligible residential exposure factor is thus inferred for the former. Relatively high hair Hg burdens prevail throughout the coastal Honda Bay population, consistent with significant methyl Hg ingestion through daily fish consumption. The data presented provide no environmental or toxicological justification for immediate remedial action. Received: 14 May 1998/Accepted: 1 September 1998