BACKGROUND STUDY ON NON-RESIDUAL PHASE OF ELEMENTS IN CHANGJIANG AND HUANGHE ESTUARINE SEDIMENTS

Analysis of Zn, Cu, Pb, Co, Cr, Li, Ni, K, Al, Fe extracted by 1 mol/L HCl or 0.5 mol/LHCl/H_2O_2, showed concentrations of Zn, Cu, Pb, Co, Cr, Fe, Ni were significantly correlated with Li, Al,K, and clay. Two methods are used to indicate the background value of the non-residual phase of elementsin sediments, and are the same as the methods used to indicate the background value of totalconcentrations in sediments. The first method uses correlograms and regression equations,the second usesthe mean element concentrations normalized with grain size. Li, Al, K can be used as reference elements to determine the background value of Zn, Cu, Pb, Co,Cr, Ni, Fe, while the clay concentration's correlation with some extractable concentrations can be used tocalculate the background value of the non-residual phase of elements as a percentage of clay concentrationin the sediments. Based on this study, the concept of using the background value of the non-residualphase of elements to compare the pollution level in differ     

Speciation of trace metals in sediments of a tropical estuary

Axial surveys were performed in the two river tributaries of the Cochin estuary, SW India during November 1988. Surficial sediments were subjected to sequential chemical extractions to delineate five metal fractions, namely, exchangeable, carbonate bound, easily reducible, organic/sulfide bound, and residual. The results indicated selective accumulation of Mn and Ni in carbonate bound and organic/sulfide forms, along with marginal amounts of Co in the exchangeable fraction. Large portions of Fe and Cr occurred in the residual fraction, whereas composite fractionation of Zn species was noticed. The exchangeable fractions of Fe and Cr as well as of easily reducible cobalt were below detection limits. The levels of Cr and Zn indicate anthropogenic inputs in this estuary, whereas Co and Ni show regional contamination exceeding natural levels. The analytical speciation procedure helps to deduce the sedimental diagenetic processes in the estuarine environment.     

Hysteresis‐based analysis of overland metal transport

Introducing a concept of equivalent mass depth of flow, this study describes the phenomenon of non‐point source pollutant (metal) transport for pavement (or overland) flow in analogy with wave propagation in wide open channels. Hysteretic and normal mass rating curves are developed for runoff rate and mass of 12 dissolved and particulate‐bound metal elements (pollutants) using the rainfall‐runoff and water quality data of the 15 × 20 m² instrumented pavement in Cincinnati, USA. Normal mass rating curves developed for easy computation of pollutant load are found to be of a form similar to Manning's, which is valid for open channel flows. Based on the hysteresis analysis, wave types for dissolution and mixing of particulate‐bound metals are identified. The analysis finds that the second‐order partial‐differential equation normally used for metal transport does not have the efficacy to describe fully the strong non‐linear phenomena such as is described for various metal elements by dynamic waves. In addition, the proportionality concept of the popular SCS‐CN concept is extended for determining the potential maximum metal mass M_p of all the 12 elements transported by a rain storm and related to the antecedent dry period (ADP). For the primary metal zinc element, M_p is found to increase with the ADP and vice versa. Copyright © 2003 John Wiley & Sons, Ltd.     

Distribution and fluxes of metals in the St. Lawrence River from the outflow of Lake Ontario to Québec City

Six anchor stations in the St. Lawrence River from the outflow of Lake Ontario to Quebec City, were occupied for ca. 24 hours in June 1987 during low flow conditions. Samples of water and suspended particulate matter were separated by continuous-flow centrifugation, and were collected every two hours.During this sampling period, fluxes of dissolved forms of zinc, copper and nickel increased in Lac St. François and downstream relative to the sum of the fluxes for the two upstream stations at the outflow of Lake Ontario. Increases in the flux of dissolved zinc and copper were pronounced below Montreal and above Lac St. Pierre. For particulate forms of metals, all five metals show that there are significant inputs in the section of the St. Lawrence River between Lac St. François and the station just above the entrance to Lac St. Pierre.The average concentrations of dissolved cadmium, lead, zinc, copper and nickel ranged from 7–23 ng/l; 9–35 ng/l; 0.434–0.939 g/l; 0.15–0.89 g/l and 0.58–1.12 g/l respectively.Regression analysis of the dissolved and particulate metal concentrations suggests that the concentration of dissolved cadmium, lead, zinc and nickel can be predicted from the regression equation and the determination of particulate metal concentration. This prediction appears to be independent of the suspended particulate matter concentration which varies from ca. 1 to 10 mg/l from the outflow of Lake Ontario to Québec City.     

Trace element distribution among rock-forming minerals from metamorphosed to partially molten basic igneous rocks in a contact aureole (Fuerteventura, Canaries)

Low pressure partial melting of basanitic and ankaramitic dykes gave rise to unusual, zebra-like migmatites, in the contact aureole of a layered pyroxenite–gabbro intrusion, in the root zone of an ocean island (Basal Complex, Fuerteventura, Canary Islands). These migmatites are characterised by a dense network of closely spaced, millimetre-wide leucocratic segregations. Their mineralogy consists of plagioclase (An_32–36), diopside, biotite, oxides (magnetite, ilmenite), +/− amphibole, dominated by plagioclase in the leucosome and diopside in the melanosome. The melanosome is almost completely recrystallised, with the preservation of large, relict igneous diopside phenocrysts in dyke centres. Comparison of whole-rock and mineral major- and trace-element data allowed us to assess the redistribution of elements between different mineral phases and generations during contact metamorphism and partial melting.

Dykes within and outside the thermal aureole behaved like closed chemical systems. Nevertheless, Zr, Hf, Y and REEs were internally redistributed, as deduced by comparing the trace element contents of the various diopside generations. Neocrystallised diopside – in the melanosome, leucosome and as epitaxial phenocryst rims – from the migmatite zone, are all enriched in Zr, Hf, Y and REEs compared to relict phenocrysts. This has been assigned to the liberation of trace elements on the breakdown of enriched primary minerals, kaersutite and sphene, on entering the thermal aureole. Major and trace element compositions of minerals in migmatite melanosomes and leucosomes are almost identical, pointing to a syn- or post-solidus reequilibration on the cooling of the migmatite terrain i.e. mineral–melt equilibria were reset to mineral–mineral equilibria.     

The geochemistry of gem opals as evidence of their origin

Seventy-seven gem opals from ten countries were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) through a dilution process, in order to establish the nature of the impurities. The results are correlated to the mode of formation and physical properties and are instrumental in establishing the geographical origin of a gem opal. The geochemistry of an opal is shown to be dependant mostly on the host rock, at least for examples from Mexico and Brazil, even if modified by weathering processes. In order of decreasing concentration, the main impurities present are Al, Ca, Fe, K, Na, and Mg (more than 500 ppm). Other noticeable elements in lesser amounts are Ba, followed by Zr, Sr, Rb, U, and Pb. For the first time, geochemistry helps to discriminate some varieties of opals. The Ba content, as well as the chondrite-normalized REE pattern, are the keys to separating sedimentary opals (Ba > 110 ppm, Eu and Ce anomalies) from volcanic opals (Ba < 110 ppm, no Eu or Ce anomaly). The Ca content, and to a lesser extent that of Mg, Al, K and Nb, helps to distinguish gem opals from different volcanic environments. The limited range of concentrations for all elements in precious (play-of-color) compared to common opals, indicates that this variety must have very specific, or more restricted, conditions of formation. We tentatively interpreted the presence of impurities in terms of crystallochemistry, even if opal is a poorly crystallized or amorphous material. The main replacement is the substitution of Si⁴⁺ by Al³⁺ and Fe³⁺. The induced charge imbalance is compensated chiefly by Ca²⁺, Mg²⁺, Mn²⁺, Ba²⁺, K⁺, and Na⁺. In terms of origin of color, greater concentrations of iron induce darker colors (from yellow to “chocolate brown”). This element inhibits luminescence for concentrations above 1000 ppm, whereas already a low content in U (≤ 1 ppm) induces a green luminescence.     

Modeling on adsorption–desorption of trace metals to suspended particle matter in the Changjiang Estuary

The uptake and release of trace metals (Cu, Ni, Zn, Cd, and Co) in estuaries are studied using river and sea end-member waters and suspended particulate matter (SPM) collected from the Changjiang Estuary, China. The kinetics of adsorption and desorption were studied in terms of environmental factors (pH, SPM loading, and salinity) and metal concentrations. The uptake of the metals studied onto SPM occurred mostly within 10 h and reached an asymptotic value within 40 h in the Changjiang Estuary. As low pH river water flows into the high pH seawater and the water become more alkaline as it approaches to the seaside of estuary, metals adsorb more on SPM in higher pH water, thus, particulate phase transport of metal become increasingly important in the seaward side of the estuary. The percentage of adsorption recovery and the distribution coefficients for trace metals remained to be relatively invariable and a significant reduction only occurred in very high concentrations of metals (>0.1 mg L⁻¹). The general effect of salinity on metal behavior was to decrease the degree of adsorption of Cu, Zn, Cd, Co, and Ni onto SPM but to increase their adsorption equilibrium pH. The adsorption–desorption kinetics of trace metals were further investigated using Kurbatov adsorption model. The model appears to be most useful for the metals showing the conservative behavior during mixing of river and seawater in the estuary. Our work demonstrates that dissolved concentration of trace metals in estuary can be modeled based on the metal concentration in SPM, pH and salinity using a Kurbatov adsorption model assuming the natural SPM as a simple surfaced molecule.     

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.     

Soil contamination from urban and industrial activity: example of the mining district of Linares (southern Spain)

The Linares region (southern Spain) has been subjected to two important sources of pollution: the intensive mining works and the urban-industrial activity. To obtain a geochemical characterisation of the soil, 31 trace elements were analysed and 669 soil samples were collected. By means of clustering analysis, we identified groups of elements and grid squares in which relations could be established concerning soil lithology, urban and industrial activities and the degree of pollution impact; in addition, we were able to characterise the geochemical background of the study area. The multivariate study led us to identify four factors. Particularly important was factor 2, which represented the elements associated with mineral paragenesis (Cu, Pb, As, Co, Mn, Zn, Sn, Ba). This factor also contains elements related with an urban-industrial activity, such as Pb, Cu, Zn, As and Ba. Furthermore, we identified factor 4, associating Ni, V and Cr, and which is related to the use of fuels.