Diel variation of arsenic,molybdenum and antimony in a stream draining natural As geochemical anomaly

The Mokrsko Stream in the central Czech Republic is an oxic and slightly alkaline stream that drains a natural As geochemical anomaly. Although long-term monitoring has characterized the general seasonal trends in trace element concentrations (i.e., As, Mo, Cu, Zn) in this stream, little is known about solubility controls and sorption processes that influence diel cycles in trace element concentrations. Trace elements (including As species, Cu, Mn, Mo, Pb and Sb) and other parameters were monitored over two 24-h periods in unfiltered and filtered (0.1 μm) samples collected in August 2010 and June 2011. Copper and Pb were predominantly (>92% of the mass) associated with the particulate fraction (>0.1 μm). Arsenic, Mo and Sb were predominantly (>88% of the mass) in the “dissolved” (<0.1 μm) form. Particulate-associated elements displayed up to a factor of 13 differences between minimum and maximum concentrations, most likely due to increased streamflow related to rainfall events. Dissolved concentrations of the trace metal cations (Cu, Fe, Mn and Pb) were consistently low and displayed no diel trends. Dissolved As(V), Mo and Sb varied on a diel cycle, with increased concentrations (up to 36%) during the late afternoon and decreased concentrations during the nighttime. Diel trends in trace anionic elements are explained by temperature-dependent sorption, as the diel changes in pH during base flow were very small (0.07 std. units). Very low concentrations of As(III), which have been shown to vary in a diel cycle, were attributed to enhanced hydraulic exchange with As(III)-rich hyporheic water during rainfall events.     

Investigating high zircon concentrations in the fine fraction of stream sediments draining the Pan-African Dahomeyan Terrane in Nigeria

Sixteen hundred stream sediments (<150 μm fraction) collected during regional geochemical surveys in central and SW Nigeria have high median and maximum concentrations of Zr that exceed corresponding Zr concentrations found in stream sediments collected from elsewhere in the World with similar bedrock geology. X-ray diffraction studies on a sub-set of the analysed stream sediments showed that Zr is predominantly found in detrital zircon grains. However, the main proximal source rocks (Pan-African ‘Older Granites’ of Nigeria and their Proterozoic migmatitic gneiss country rocks) are not enriched in zircon (or Zr). Nevertheless, U–Pb LA-ICP-MS dating with cathodoluminescence imaging on detrital zircons, both from stream sediment samples and underlying Pan-African ‘Older Granites’ confirms a local bedrock source for the stream sediment zircons. A combination of tropical/chemical weathering and continuous physical weathering, both by ‘wet season’ flash flooding and ‘dry season’ unidirectional winds are interpreted to have effectively broken down bedrock silicate minerals and removed much of the resultant clay phases, thereby increasing the Zr contents in stream sediments. The strong correlation between winnowing index (Th/Al) and Zr concentration across the study area support this interpretation. Therefore, ‘anomalous’ high values of Zr, as well as other elements concentrated in resistant ‘heavy’ minerals in Nigeria’s streams may not reflect proximal bedrock concentrations of these elements. This conclusion has important implications for using stream sediment chemistry as an exploration tool in Nigeria for primary metal deposits associated with heavy minerals.     

The environmental impact of Aguilar mine on the heavy metal concentrations of the Yacoraite River,Jujuy Province,NW Argentina

The Yacoraite River and its tributaries run down the eastern slope of the Aguilar Range. It is one of the tributaries of the Rio Grande, located in Quebrada de Humahuaca, a UNESCO World Heritage site. The Aguilar underground mine (Pb–Ag–Zn) is located in the upper reaches of the Yacoraite River drainage basin. The aim of this work is to characterize the presence of heavy metals in water and sediments of the Yacoraite River and to identify their sources. The analysis shows the seasonal variation of heavy metals concentration in water and their relation with the World Health Organization (WHO) limits established for human consumption. The Yacoraite basin is naturally anomalous in some metals and some elements, such as As which is controlled by the chemical composition of regional lithology. During the wet season, Al, Co, Mo and Pb concentrations in water samples are higher than during the dry season; in addition, these metals are also higher than WHO limit values. High enrichment factors for Ba, Mo, Pb, Zn and Cd were found in Casa Grande stream, indicating the direct influence of the mining activities. Cd, Pb and Zn are present in the Aguilar ore minerals, such as sphalerite and galena. Sediments collected during the dry season show a drastic increase in the concentration of As, Pb, Ba, Zn, Cd and Mn. The Müller geo-accumulation index in Casa Grande indicates that it is a highly polluted stream. The concentrations of As, Pb, Ba, Zn, Cd are also high in Yacoraite River: Security Quality Guidelines indicates toxicity. A decrease in enrichment factors and geo-accumulation indices observed in sediments indicates the occurrence of precipitation/adsorption processes in the river to restore the equilibrium composition. Strict environmental controls in Aguilar Mine are necessary to avoid the uncontrolled input of toxic metals in Casa Grande stream and Yacoraite River.     

Particulate trace metal speciation in stream sediments and relationships with grain size: Implications for geochemical exploration

Sediment samples were collected from streambeds in an undisturbed watershed in eastern Quebec (Gaspé Peninsula). Two sampling sites were located on a stream draining an area of known mineralization (Cu, Pb, Zn) and two on a control stream. The sediment samples were separated into 8 distinct size classes in the 850 μm to <1 μm size range by wet sieving, gravity sedimentation or centrifugation. Each sediment subsample was then subjected to a sequential extraction procedure designed to partition the particulate heavy metals into five fractions: (1) exchangeable; (2) specifically adsorbed or bound to carbonates; (3) bound to Fe-Mn oxides; (4) bound to organic matter; (5) residual. The following metals were analyzed in each extract: Cu, Pb, Zn; Fe, Mn.Comparison of samples from the mineralized area with control samples revealed the expected increase in total concentrations for Cu, Pb and Zn. Non-detrital metals were mainly associated with Fe oxides (specifically adsorbed; occluded) and with organic matter or resistant sulfides. For a given sample, variation of trace metal levels in fractions 2 and 3 with grain size reflected changes in the available quantities of the inorganic scavenging phase (FeOx/MnOx); normalization with respect to Fe and Mn content in fraction 3 greatly reduced the apparent dependency on grain size.The results of this study suggest that a single reducing extraction (NH₂OH.HCl) could be used advantageously to detect anomalies in routine geochemical surveys. A second leaching step with acidified H₂O₂ could also be included, as the trace metal concentrations in fraction 4, normalized with respect to organic carbon content, also showed high {anomaly/background} ratios.     

Hydrological and geochemical controls governing the distribution of trace metals in a mine-impacted lake

Factors controlling the distribution of mining-derived Cu, Pb and Zn in the waters and bottom sediments of a large Andean lake (Lago Junin, Peru) have been assessed based on sample collections in May/June 1997 (dry season) and February/March 1998 (wet season). Relatively low levels of trace metals detected in surface waters of the lake during the dry season contrasted greatly with the high values observed during the wet period. Dry season concentrations of total Zn, Cu and Pb in the central lake basin averaged 41, 4.4 and 0.24 µg/L, respectively. In contrast, the respective wet season concentrations of total Zn, Cu and Pb in areas of the main basin ranged up to 387, 52 and 40 µg/L. The seasonal variability in metal concentrations largely reflects an increase in the concentration of particulate metal phases during the wet season. Such observations can be attributed to changes in sediment loadings associated with mining-derived river inputs and changes in lake circulation resulting from hydroelectric dam operations. Surface sediments are characterized by lake-wide enrichments of Zn, Cu and Pb, with maximum concentrations reaching as high as 5, 0.25 and 0.7 wt%, respectively. Estimated rates of authigenic metal accumulation are not sufficient to account for the elevated metal concentrations in the main basin of the lake, indicating that metal distributions are governed by the accumulation of metal-rich particulates. Variations in the spatial distributions of Zn, Cu and Pb are suggested to be a function of varying host phases and textural sorting.     

Sedimentological characteristics, heavy metal distribution and magnetic properties in subtidal sediments, Ria de Pontevedra, NW Spain

The rias of NW Spain are coastal ecosystems of high biological productivity and great economic importance. They are intensively exploited by man for fish and shellfish. There are a number of important centres of population and industrial activity along their margins, which serve as sources of contamination. In this context, it is desirable to achieve the best possible understanding of the physico‐chemical processes that control spatial and temporal variations in the geochemical, mineralogical and sedimentological characteristics of near‐surface sediments in the Ria de Pontevedra and, in particular, the distribution and mobility of heavy metal contaminants. Thus, adequate environmental planning can be achieved for this site and understanding gained for comparable contexts. Core samples were examined from the inner, middle and outer parts of the ria. Grain‐size distributions reflect the presence of two main populations, one dominated by silt and clay, derived mainly from terrestrial sources, and the other by fine sand to coarse silt, which is derived mainly from continental shelf and ria mouth sources. Mineralogical analysis shows an abundance of terrestrial intensive‐weathering products near the ria head, a dominance of shelf‐derived sediment towards the mouth and the presence of several diagenetic minerals whose nature varies with location within the ria. In the inner ria, the near‐surface sediments are slightly enriched in Pb, Cu and Zn from anthropogenic sources. These sediments are fine grained and have a high organic content; hence, they have a higher potential to sorb contaminants than the coarser grained, less organic‐rich sediments of the mid and outer ria. The estimated sedimentation rates for the fine‐grained organic‐rich sediments from the inner part of the ria are about 1 mm year^–1. The dominant authigenic minerals in the inner ria are iron sulphides, whereas in the mid and outer ria, iron silicates and oxyhydroxides are more important. These differences in authigenic iron mineralogy are clearly reflected by the magnetic properties of the sediments.     

Historical analysis of heavy metal pollution in three estuaries on the north coast of Galicia (NW Spain)

This research focuses on the development of metal pollution in sediment cores from three estuaries in Northwest Spain: Viveiro, Ortigueira and Barqueiro. Pb, Cu, Co, Cr, Cd and Zn and total organic carbon were assessed using principal component analysis (PCA) in order to obtain background values, measure pollution levels and identify pollution sources. Results were interpreted by considering the local industrial history, grain size and C/N relationship. The pollution levels obtained bear a strong resemblance to those documented for of a moderately industrialised area. PCA identifies factors that reflect mainly temporal associations with metals. Sedimentation rates between 0.9 and 1.1 cm/year were determined. In Viveiro core levels of Cr pollution are associated with tanneries. In Ortigueira, high core levels of Cu and Co are linked to mining, and Cr levels to adjacent ultramafic rocks. Erosion of Holocene sediment causes high values of Co and Cr in the Barqueiro core. Cu increase in the three estuaries is related to fungicide use since 1910. Sea level rise appears to be affecting the marine characteristics of the sediments in Barqueiro. In Viveiro, the nature of the sediment reflects engineering work and land reclamation.     

Early Miocene post-collisional magmatism in NW Turkey: geochemical and geochronological constraints

The Alaçam region of NW Turkey lies within the Alpine collision zone between the Sakarya continent and the Menderes platform. Four different tectonic zones of these two continents form imbricated nappe packages (including the Afyon zone), intruded by the Alaçam granite. Newly determined U-Pb zircon ages of this granite are 20.0 ± 1.4 and 20.3 ± 3.3 Ma, indicating early Miocene emplacement. Rb-Sr biotite ages of the granite are 20.01 ± 0.20 and 20.17 ± 0.20 Ma, suggesting fast cooling at a shallow crustal level. Geochemical characteristics show that the Alaçam granite is similar to numerous EW-trending plutons in NW Anatolia.

Gneissic granites of the Afyon tectonic zone were intruded by the Miocene Alaçam granite and have been interpreted in earlier studies as sheared parts of the Alaçam granite, which formed along a crustal-scale detachment zone under an extensional regime. We determined a U-Pb zircon age of 314.9 ± 2.7 Ma for a gneissic granite sample of the Afyon zone, demonstrating that these rocks are unrelated to the Miocene Alaçam granite. The early Miocene granitic plutons bear post-collisional geochemical features and are interpreted as products of Alpine-type magmatism along the Izmir–Ankara suture zone in NW Turkey, and seem to have no genetic relation to the detachment zone.     

Artificial geochemical barriers for environmental improvement in a coal basin region

In the Urals (Russia), in the territory of the closed Kisel Coal basin acid mine water is a source of contamination. The authors suggest using artificial geochemical barriers as an efficient method for environmental improvement in this coal basin region. Alkaline waste products were used for barrier creation. Waste products are non-toxic and consist of 70–80 % calcite (CaCO₃). According to tests they are capable of neutralizing mine water and to precipitate iron, aluminum, heavy metals. The scientific basis for the creation of geochemical barriers for environmental improvement is presented.     

Stratigraphic sequence, elemental concentrations and heavy metal pollution in Holocene sediments from the Tinto-Odiel Estuary, southwestern Spain

 The Holocene filling of the Tinto-Odiel Estuary comprises seven lithofacies over a Mio-Pliocene substrate. The sequence includes three system tracts: lowstand system (10 000 to 8700 years BP), transgressive system (8700 to 7000 years BP), and regressive system (7000 to Recent). Twenty sediment samples from the 50-m borehole were analyzed for their major components and minor element concentrations. Two multivariate analysis methods, principal component analysis and cluster analysis, were performed in the analytical data set to help visualize the sample clusters and the element associations. Samples corresponding to unpolluted, pre-mining sediments are clearly separated by cluster analysis, mainly as a result of the low content in sulphide-associated heavy metals such as Cu, Zn, As, Ag, and Pb. So, these sediments may be utilized as a background for geochemical analysis (bulk sample) in other adjacent estuaries, both in sandy and silty-clayey sediments. As a consequence of large-scale mining and smelting operations occurred since prehistoric times on the river banks, a rapid rise in the metal pollution was found in the upper 2.5 m of the natural filling, with values exceeding up to ten times the natural background levels. In addition, since the mid-1960s, large amounts of waste and pollutant effluents have been discharged from industries located around the estuary, increasing the heavy metal content in the last 0.3 m of the natural sedimentation. Received: 18 August 1997 · Accepted: 19 January 1998     

Reconnaissance geochemical survey in the Marahiq area,Wadi Allaqi region,south Egypt: a preliminary assessment of stream sediments for gold placer and environmental hazard

The Marahiq area represents a portion of the Pan-African belt from the Neoproterozoic age in south Egypt and includes metamorphosed ultramafic rocks, metavolcanic rocks, and granodiorite pluton. The area is characterized by the ancient abandoned Au mine and the recent active talc mines. The present paper provides a preliminary assessment of stream sediments for gold (Au) placer and environmental hazard. Steam sediments from 36 stations were analyzed using ICP-MS for determining the concentration of 53 elements. Various statistical techniques, graphical representations, a set of complementary sediment quality assessment methods, and different mapping methods have been applied. The results showed that Au and the investigated elements were influenced by long history of the ancient mining activities and weathering processes, leading to elevate Au and some heavy metal(loid)s concentrations and exhibit enrichment ratios as follows: Te > As > Au > Cu > Cd > Co > Ni > V. Whereas Cd, Co, and V were attributed to geogenic origin, As, Au, Cu, Ni, and Te were derived from anthropogenic mining activities. It is found that the anomalies of Au and the element of interest are indicative of Au placer and point out a new perspective Au-sulfide mineralization hosted along the favorable tectonic zones that were the main source of Au placer. Both As and Te are good pathfinders to explore Au placer and related mineralization. Environmentally, the excess of As, Cu, Ni, and Te could generate moderate levels of contamination and low level of ecological risk in the sediments. Although As, Cu and Ni posed medium–low potentially adverse effects and low toxicity levels, they cannot cause harmful influences on biological life. Accordingly, streambed sediments are considered as safe and acceptable as inoffensive materials for environmental management. Overall, this study is as reference values for governmental organizations for appraising future environmental pollution in the area. Also, it is fruitful for Au placer and promising with success for Au exploration along the shear zones and strike-slip faults.     

Historical backcasting of metal concentrations in the Chattahoochee River, Georgia: Population growth and environmental policy

The impact of increasing urbanization on the quality of a river system has been investigated by examining the current concentration of trace metals in the Chattahoochee River south of Atlanta, GA, and comparing these to previously published historical sediment data from reservoirs along the river. The lack of historical data for dissolved metal concentrations prior to 1980 requires an approach using these historic metal data from sediment cores. Core data are combined with current suspended load and dissolved metal data to “backcast” dissolved metal concentrations in the metro-Atlanta portion of the Chattahoochee River. The data suggest that the per capita input of dissolved trace metals have actually decreased since the 1920s, but anthropogenic inputs of metal are still a substantial water quality issue.     

8000 yr of black carbon accumulation in a colluvial soil from NW Spain

Analytical pyrolysis-GC/MS and solid-state ¹³C NMR (nuclear magnetic resonance) were applied to the NaOH-extractable organic matter fraction of a colluvial soil from Galicia (NW Spain) that represents more than 8500 yr of accumulation. While molecular indicators of vegetation change were looked for, it seemed likely that any such signal was disturbed by the intense fire regime of the area. This conclusion was drawn from (1) the presence of three charcoal layers, (2) the high proportion of aryl C in NMR spectra (non-quantitative) and (3) the prevalence of benzenes and polycyclic aromatic hydrocarbons (PAHs) in the chromatograms (38 ± 6% of total identified peak area), also in charcoal-poor samples. If this conclusion is accurate, the area has been subjected to burning episodes for at least 8000 yr. Additionally, the results indicate that biomass burning residues (black carbon; BC) may become NaOH extractable after long periods of degradation in mineral soil. These results add to our knowledge of the long-term fate of BC in soil, which is a potential agent in the global C cycle.     

A seeping sea-floor in a Ria environment: Ria de Vigo (NW Spain)

 The occurrence of gas accumulations in the Ría de Vigo (NW Spain) have been characterized by the authors in previous research. Pockmarks frequently appear on seismic and sonar records, covering ca. 45% of the sea-floor of the study area, which indicates that gas expulsion is not an uncommon phenomena in the coastal Ría environment. Here we report the occurrence of gas seepage for the first time along the coast of NW Spain. Side-scan sonar, echo-sounder and high-resolution seismic techniques, were used for mapping gas-expulsion features. Some expulsion pockmarks sit over elongated features that represent bottom marks created by anthropogenic activity. Thus, these anthropogenic sites may act as preferential venting zones for gas, as well as being potential hazards on a muddy sea-bed such as that of the Ría where gas accumulates just below the surface of the sea-floor. Received: 25 May 1998 · Accepted: 20 November 1998     

Geochemical controls on lead concentrations in stream water and sediments

The equilibrium distribution of lead in solution and adsorbed on cation exchange sites in sediment theoretically may be calculated from equations representing selectivities of substrate for lead over H⁺, Ca²⁺ and Na⁺, and the stabilities of lead solute species. Such calculations include consideration of total concentrations of major ions, cation exchange capacity (CEC) of substrate, and pH, at values expected in various natural systems. Measurements of CEC and selectivity coefficients were made for synthetic halloysite, a finely divided amorphous 1:1 clay prepared by precipitation from a mixture of solutions of aluminum and silica. Where suspended sediment having the same properties is present in concentrations of 10-1,000 mg/1 at pH 6–8, more than 90% of the lead present can be adsorbed on sediment surfaces. The cation exchange behavior of lead and other minor cationic species in natural systems could be predicted by this type of model if enough other supporting information were available. Information of the type needed describing natural stream sediments, however, is presently inadequate for accurate predictions.     

Soil and stream sediment based geochemical mapping: A case study in Goa

Geochemical mapping has been carried out in Goa using soil/laterite and stream sediment as media. The geochemical maps for U, Th, Nb and Ta show a conspicuous pattern in the NW part of Goa. The anomaly axis shows a NE-SW trend which is across the formational trend. The nickel and copper distribution around Usgaon area, east of Ponda, have indicated anomalous signature in the northern continuation of the Usgaon ultramafic complex.     

Comparison of vegetation and stream sediment geochemical patterns in northeastern New South Wales

This study compares the geochemical response of stream sediments and adjacent vegetation samples, with variations in drainage catchment lithology and the occurrence of mineralisation, within a 14,000-km² block of the northeastern region of New South Wales, Australia. The area contains a range of lithologies within a Devonian–Permian accretionary complex and Mesozoic sedimentary basin, as well as a wide range of mineral deposits. Sampling was designed to confine each sub-catchment to a single lithological group (mafic and ultramafic rocks, acid intrusives, volcanics, metasedimentary and sedimentary rocks or alluvium). Leaves of over 20 genera, dominated by (Allo-)Casuarina, Eucalyptus, Acacia, Callistemon and Melaleuca, and the <250-μm fraction of the stream sediments were analysed by INAA. The uptake of most trace elements varied between genera, with Callistemon displaying the highest median As and La contents and Eucalyptus the highest Co contents. The stream sediment and vegetation geochemistry reflect both hydromorphic and mechanical dispersion within sub-catchments, with regional patterns dominant over local influences. The vegetation appears to be influenced to a greater extent by hydromorphic dispersion, as indicated by differences in the ratio of leaf to sediment Cr concentrations in sub-catchments draining serpentinites and basalts. Although most known mineral deposits in the region produced anomalies in at least one medium, there was little correlation between the trace element concentrations of the vegetation and stream sediments on a site-by-site basis. A number of Au targets were only detected on the basis of the biogeochemistry and others were only reflected in the stream sediment geochemistry. In general, vegetation displayed more extensive dispersion trains away from mineralisation than did the stream sediments. Differences in the response of the two sampling media suggest their joint use in exploration or environmental surveys to maximise the probability of detecting mineralisation.     

Influence of diurnal cycles on metal concentrations and loads in streams draining abandoned mine lands: an example from High Ore Creek,Montana

Diurnal water samples were collected simultaneously at four locations along High Ore Creek (Montana, USA), a small stream with near-neutral pH that contains elevated concentrations of Zn, Mn, Cd, and As from abandoned mines near its headwaters. During the same time period, two sets of synoptic samples were collected by workers moving in opposite directions along the stream. Large diurnal fluctuations in Zn concentration were found at three of the 24-h monitoring stations, but not at the outlet to a settling pond. Because the concentrations of Zn were dropping at most locations in the creek during the day (in response to the daily cycle of day-time attenuation and night-time release), the synoptic sampler who moved upstream obtained a data set that led to the conclusion that Zn load increased with distance downstream. The sampler who moved in a downstream direction obtained the opposite results. Thus, failure to take short-term diurnal cycling into account can lead to incorrect conclusions regarding spatial or temporal trends in water quality within a watershed.     

Heavy metal content in the stream sediments adjacent to a sanitary landfill

Samples of stream sediments were collected along two streams adjacent to a sanitary landfill. One of the streams drained the landfill directly. In addition, control of background samples were also analyzed from a stream not affected by the landfill. All samples were analyzed for Ag, Zn, Cu, Cd, and Pb content using atomic adsorption techniques. The pH of the three streams were monitored since pH differences in the streams may affect the quantities of metals adsorbed or precipitated on the sediments. The comparison between the content of Ag, Zn, and Cu in the sediments of the two study streams and the same metals in the control sediments indicated the landfill emitted these metals into the two adjacent streams. However, since the Cd and Pb contents in the sediments of both streams were similar to that of the control stream sediments, these metals may not be emitted into the two study streams from the landfill and they represent only background quantities. The comparisons of each metal in the sediments of each stream were made by the use of a metal trend chart, the individual calculated mean metal content values, and by the statistical two sample t-test. No decreasing trends of the quantities of Ag, Zn, or Cu as a function of increasing distance from the landfill was present in the sediments along the stream that drained the landfill directly. These sediments might have been affected by stream action and became mixed with other sediments downstream.