Distribution of trace elements in the coastal sea sediments of Maslinica Bay, Croatia

Spatial distributions of trace elements in the coastal sea sediments and water of Maslinica Bay (Southern Adriatic), Croatia and possible changes in marine flora and foraminifera communities due to pollution were investigated. Macro, micro and trace elements’ distributions in five granulometric fractions were determined for each sediment sample. Bulk sediment samples were also subjected to leaching tests. Elemental concentrations in sediments, sediment extracts and seawater were measured by source excited energy dispersive X-ray fluorescence (EDXRF). Concentrations of the elements Cr, Cu, Zn, and Pb in bulk sediment samples taken in the Maslinica Bay were from 2.1 to over six times enriched when compared with the background level determined for coarse grained carbonate sediments. A low degree of trace elements leaching determined for bulk sediments pointed to strong bonding of trace elements to sediment mineral phases. The analyses of marine flora pointed to higher eutrophication, which disturbs the balance between communities and natural habitats.     

Authigenic associations between selected rare earth elements and trace metals in lacustrine sediments

Surficial sediment samples were collected at 47 stations in Little Traverse Bay, Lake Michigan, to determine the geochemical associations between certain rare earth elements (REE's) and trace metals. Each sample was analyzed for carbonate carbon, organic carbon, grain size, and the elements Al, Ca, Ce, Co, Cr, Eu, Fe, Hf, La, and Mn. Two distinct Ce subpopulatins were identified by graphical analysis, and an R-mode factor analysis was applied to data from the “enriched” Ce subpopulation (18 samples). Results show that the REE's and trace metals are primarily enriched in the authigenic phase of these sediments. Partial correlation analyses indicate that the REE's are primarily associated with hydrous Fe oxides relative to organic matter in this phase. The ratio of Ce/La concentrations increased markedly from the bay margins to the central trough of the bay, indicating that Ce, similar to Fe, exhibits a variable oxidation state in the authigenic phase of nearshore fine-grained sediments. The results of the present study suggest that the REE's and trace metals behave coherently in the authigenic phase of recent lacustrine sediments, and the REE's may be useful as geochemical tracers to differentiate between trace metal enrichments in surface sediments as a result of diagenesis and pollution loadings.     

Minor elements in sediments of Great Bay estuary,New Hampshire

Concentrations of copper, zinc, chromium, lead, cadmium, and phosphorus were obtained from 81 samples of unconsolidated estuarine sediment from Great Bay, New Hampshire. Dispersal of aqueous chromium from localized industrial effluent is believed responsible for an increase in sediment chromium throughout the entire estuary. High phosphorus concentrations exist in sediment near the outfalls from several waste-water treatment plants. There is no evidence for any increase of copper, zinc, lead, or cadmium in this estuary, except for localized high concentrations close to industrial outfalls. Fine-grained sediments and organic carbon correlate highly with all the elements studied, except for chromium. This suggests that conventional agents of sedimentary adsorption are not adequate to explain the incorporation of chromium into sediment under the conditions of heavy industrial discharge which exist in this estuary. Sediment phosphorus correlates highly with minor elements, suggesting that it is an adsorption agent, similar to more typical sedimentary parameters such as organic matter and clay minerals. In such a capacity phosphorus may enhance the sedimentary uptake of other aqueous species, and account for higher chromium sediment concentrations. Comparative data from other sedimentary environments emphasize the environmental significance of these elements in Great Bay.     

Distribution,chemical speciation and source of trace elements in surface sediments of the Changjiang Estuary

To evaluate biogeochemical characteristics, eco-environmental risks and sources of trace elements (TEs: As, Hg, Se, Sb, Te, Sn, Bi and Ge), their total concentrations and chemical speciation in surface sediments collected from the Changjiang Estuary were determined. Total concentrations for As, Hg, Se, Sb, Te, Sn, Bi and Ge were 4.57–30.20, 0.01–0.40, 0.04–0.38, 0.36–1.48, 0.02–0.10, 0.48–6.58, 0.13–0.64 and 0.83–2.43 μg/g, respectively, with higher values at the estuary. This distribution pattern was attributed to the riverine input and high clay and total organic carbon contents. The sequential extraction suggested that TEs mainly occurred in residual fractions. The risk assessment code suggested that As, Hg and Sn were at low risk, whereas Bi, Se, Sb, Te and Ge were at medium risk. The geoaccumulation index (I _geo) and principal component analysis indicated that Se and Sn mainly came from the natural input (crustal and biological inputs), whereas As, Sb, Hg, Bi and Te came from both of the crustal and anthropogenic inputs via atmosphere and rivers. In addition, Ge possibly came from the natural (crustal and biological inputs) and anthropogenic inputs.     

Distribution and geochemistry of selected trace elements in the lignites of Cambay basin,Gujarat, western India

In the present investigation all the working lignite seams of Cambay basin of Gujarat have been studied to see the distribution and geochemistry of selected major/minor elements like Fe, Ca, Na, K, Mg, and Mn and trace elements like Cu, Co, Cr, Cd, Ni, Pb and Zn. The vertical variation of these elements along the seam profiles has been studied to see the pattern of distribution of these elements and also to know the horizons of their enrichment and the probable cause. Further, these elements have been correlated among themselves and also with organic and inorganic matter of lignite. The correlation study indicates that in Tadkeshwar upper seam Fe has its affinity with huminite while Mg and Na have their affinity with liptinite and in Tadkeshwar lower seam Na has an affinity with liptinite. In Vastan upper seam Mn and Cu are associated with inertinite and Na with huminite while in Vastan lower seam Cu relates to huminite and Cd to liptinite and huminite. In Rajpardi seam Ca and Co are associated with huminite. The study provides information on the mode of occurrence of elements of less studied lignites of western India.     

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.     

Distribution of arsenic and other trace elements in the Holocene sediments of the Meghna River Delta, Bangladesh

Geochemical study of the Holocene sediments of the Meghna River Delta, Chandpur, Bangladesh was conducted to investigate the distribution of arsenic and related trace and major elements. The work carried out includes analyses of core sediments and provenance study by rare earth element (REE) analysis. Results showed that the cores pass downward from silty clays and clays into fine to medium sands. The uppermost 3 m of the core sediments are oxidized [average oxidation reduction potential (ORP) + 230 mV], and the ORP values gradually become negative with depths (−45 to −170 mV), indicating anoxic conditions prevail in the Meghna sediments. The REE patterns of all lithotypes in the study areas are similar and are comparable to the average upper continental crust. Arsenic and other trace elements (Pb, Zn, Cu, Ni, and Cr) have greater concentrations in the silts and clays compared to those in the sands. Positive correlation between As and Fe was found in the sediments, indicating As may be adsorbed on Fe oxides in aquifer sediments.     

Regional geochemistry of trace elements in Chesapeake Bay sediments

The concentrations of Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb in 177 surface sediment samples from throughout Chesapeake Bay are reported. Analyses were made of both unfractionated samples and the <63 μm fractions. Analytical uncertainty, always less than ±10%, controlled reproducibility in analyses of the <63 μm fractions, but sampling variance controlled reproducibility in the unfractionated samples, especially when coarse-grained sediments were being analyzed. Sediments in the northernmost part of the bay are enriched relative to average continental crust in all elements except Cr. This reflects the composition of dissolved and suspended material being delivered to that region by the Susquehanna River. The enriched sediments appear not to be transported south of Baltimore in significant quantily. Zinc, cadmium, and lead are enriched relative to average crust throughout the bay and in most other estuaries in the eastern United States.     

Heavy metals and polychlorinated biphenyls in sediments of the Yangtze river estuary,China

Typical pollutants in sediments from 22 sampling sites of the Yangtze river estuary in 2006 were investigated in the present study. Arsenic, mercury, cadmium, copper, chromium, zinc, lead, and polychlorinated biphenyls of the Yangtze river estuary sediments were found as 6.49–17.6, 0.0164–0.0987, 0.059–0.319, 11.7–46.6, 10.5–113, 44.5–125, 14.8–32.7, and 0.0006–0.0026 mg/kg, respectively. Results indicated the presence of a contamination in the Yangtze river estuary. Through analyzing the contents of typical pollutants in sediments with adopting the index number techniques of Muller geoaccumulation index and Hakanson ecological risk factors and index, the quality status of these sediments were evaluated. Furthermore, the potential ecological risks of the estuary were determined quantitatively. The overall environmental quality of typical pollutants was generally in a good condition in most sites. The results showed that arsenic was the main environmental pollution factor, and cadmium was the main potential ecological factor. The highest potential ecological risk index appeared in the south branch of the Yangtze river, which was mainly due to terrestrial pollution in Shanghai. The results of this study can be used for decision makers to prioritize measures to control the pollution for these typical pollutants.     

Stratification and bottom-water hypoxia in the Pamlico River estuary

Relationships among bottom-water dissolved oxygen (DO), vertical stratification, and the factors responsible for stratification-destratification in this shallow, low tidal-energy estuary were studied using a 15-yr set of biweekly measurements, along with some recent continuous-monitoring data. Hypoxia develops only when there is both vertical water-column stratification and warm water temperature (>15°C). In July, 75% of the DO readings were <5 mg 1^?1, and one-third were <1 mg 1^?1. Severe hypoxia occurs more frequently in the upper half of the estuary than near the mouth. Both the time series data and correlation analysis results indicate that stratification events and DO levels are tightly coupled with variations in freshwater discharge and wind stress. Stratification can form or disappear in a matter of hours, and episodes lasting from one to several days seem to be common. Estimated summertime respiration rates in the water and sediments are sufficient to produce hypoxia if the water is mixed only every 6–12 d. There has been no trend toward lower bottom water DO in the Pamlico River Estuary over the past 15 yr. *** DIRECT SUPPORT *** A01BY059 00002     

Distribution and partitioning of major and trace elements in pyrite-bearing sediments of a Mediterranean coastal lagoon

The formation of iron sulphide minerals exerts significant control on the behaviour of trace elements in sediments. In this study, three short sediment cores, retrieved from the remote Antinioti lagoon (N. Kerkyra Island, NW Greece), are investigated concerning the solid phase composition, distribution, and partitioning of major (Al, Fe) and trace elements (Cd, Cu, Mn, Pb, and Zn). According to ²¹⁰Pb, the sediments sampled correspond to depositions of the last 120 years. The high amounts of organic carbon (4.1–27.5%) result in the formation of Fe sulphides, predominantly pyrite, already at the surface sediment layers. Pyrite morphologies include monocrystals, polyframboids, and complex FeS–FeS₂ aggregates. According to synchrotron-generated micro X-ray fluorescence and X-ray absorption near-edge structure spectra, authigenically formed, Mn-containing, Fe(III) oxyhydroxides (goethite type) co-exist with pyrite in the sediments studied. Microscopic techniques evidence the formation of galena, sphalerite and CuS, whereas sequential extractions show that carbonates are important hosts for Mn, Cd, and Zn. However, significant percentages of non-lattice held elements are bound to Fe/Mn oxyhydroxides that resist reductive dissolution (on average 60% of Pb, 46% of Cd, 43% of Zn and 9% of Cu). The partitioning pattern changes drastically in the deeper part of the core that is influenced by freshwater inputs. In these sediments, the post-depositional pyritization mechanism, illustrated by overgrowths of Fe monosulphides on pre-existing pyrite grains, results in relatively high degree of pyritization that reaches 49% for Cd, 66% for Cu, 32% for Zn and 7% for Pb.     

Mobility and retention of trace elements in hardpan-cemented cassiterite tailings, north Queensland, Australia

This study reports on the mobility and retention of trace elements in cassiterite tailings at the inactive Jumna mill, tropical north Queensland. Since the 1980s, the uncapped tailings have developed laterally discontinuous Fe-rich hardpans, which are located in the higher parts of gently sloping tailings masses and at the top (<50 cm) of the tailings piles. Hardpan-cemented tailings comprise thin layers (typically ∼0.2–2 mm thick) of HFO (hydrous ferric oxides) and sulfate efflorescences cementing tailings grains. In comparison to the tailings, the hardpan-cemented tailings contain significantly higher median As, Ca, Cd, Co, Cu, Fe, In, Mn, Mo, S_total, Th, U, Y and Zn values. Partial leaching studies of tailings and pond water analyses indicate that wetting and acidification of Fe-cemented tailings removes significant proportions of trace elements into pore and surface waters. Tin shows no mobility due to the presence of weathering-resistant cassiterite (SnO₂) and, As and Pb display limited mobility possibly due to their coprecipitation with jarosite-type phases and HFO materials at the top of the tailings profile. By contrast, the trace elements Cd, Ce, Cu, La, Ni, Pb, U and Zn display the greatest mobility, possibly due to their incorporation in soluble sulfate efflorescences and sorption onto mineral and HFO surfaces. Hence, the Fe-rich hardpans do not protect the sulfidic tailings from further oxidation nor do they cause permanent sequestration of trace elements.     

Distribution and fractionation of rare earth elements and Yttrium in suspended and bottom sediments of the Kali estuary,western India

Concentrations of rare earth elements (REE) and yttrium (Y), and major metals (Al, Fe and Mn) were measured in suspended particulate matter (SPM) and bottom sediments of the Kali estuary, western India, for their distribution and fractionation. The contents of SPM and metals in it were more uniform along the longitudinal transect during the monsoon. During the post- and pre-monsoons, low SPM in the upper/middle estuary coincided with high Fe and Mn and total REE (∑REE). But in the lower estuary SPM and its ∑REE content increased seaward, while Fe and Mn decreased. The Y/Ho ratios decreased seaward during the monsoon but increased during the post-monsoon. Sm/Nd ratios were more uniform along the transect during monsoon but decreased marginally seaward in other seasons. The Post-Archean Average Australian Shale (PAAS)-normalized REE patterns exhibited middle REE and heavy REE enrichment with positive Ce (\({\text{Ce}}/{\text{Ce}}^{*}\)), Eu (\({\text{Eu}}/{\text{Eu}}^{*}\)) and Y anomalies. The \({\text{Ce}}/{\text{Ce}}^{*}\) increased but \({\text{Eu}}/{\text{Eu}}^{*}\) decreased marginally seaward. The fine-grained sediments showed higher ∑REE and lower Y/Ho ratios than in coarse-grained sediments. The PAAS-normalized REE patterns of sediment were similar to that of SPM. The results revealed two processes, colloidal flocculation and coagulation of metals in the low-salinity zone and an estuarine turbidity maximum in the high salinity zone. Rare earths and yttrium (REY) in SPM and sediments primarily reflected the source rock composition than that of chemical weathering. Apart from physico-chemical processes, the mineralogy and grain size of sediments controlled the distribution and fractionation of REY in the estuary.     

Geochemical characteristics of trace elements in sediments of Dongting Lake, central China

Although eutrophication and trace element contamination are two key environmental problems in Dongting Lake, a systematic study of the distribution of trace elements in sediments of this lake has not previously been undertaken. In order to identify the current levels of trace metal contamination in Dongting Lake, the concentrations of trace elements （Cd, Cr Cu, Ni, Pb, Zn, As and Hg） in the sediments at 53 locations were investigated in this study. The lake, the second largest fresh-water lake in China, boasts three China wetlands of international importance. Dongting Lake which lies in the south of the middle Yangtze River is the most important reservoir lake in the Yangtze River drainage area, and is characterized by fast flow-through water, large runoff volume and short period of exchanging water （no more than 20 days）. The granulometric analysis result of sediments shows that a large proportion of the sediments measures at 2-63 μm in size; the result of mineralogical analysis shows that original mineral is the main composition of the sediments, followed by clay mineral and carbonate. The contents of copper, lead, zinc, cadmium, arsenic and mercury are higher than the background levels of soil （ Ⅰ Soil） in China, but lower than the threshold values for severely polluted soil （Ⅲ Soil） in China except Cd higher than that in Ⅲ Soil. The concentrations of trace elements analyzed are higher than the Threshold Effect Level of Interim Sediment Quality Guideline by Canada EPA and are lower than the Probable Effect Level. The assessment by geoaccumulation index shows that the contamination of Cd reached strong level in Dongting Lake. Study on speciation of metals by a BCR procedure indicates that the trace elements （Cu, Zn, Cr, and Ni） analyzed are mainly distributed in residual phases but Pb in Fe/Mn oxhydroxide phase and Cd in soluble and carbonate-bound fraction. The potential risk was the highest in East Dongting Lake based on the calculated contamination factors which are mostly probably caused by the deposition of the trace element pollutants via the Xiangjiang River and the discharge of the pollution sources in the vicinity of East Dongting Lake.     

Tidal river sediments in the Washington,D.C. area. I. Distribution and sources of trace metals

Thirty-three bottom sediments were collected from the Potomac and Anacostia rivers, Tidal Basin, and Washington Ship Channel in June 1991 to define the extent of trace metal contamination and to elucidate source areas of sediment contaminants. In addition, twenty-three sediment samples were collected directly in front of and within major storm and combined sewers that discharge directly to these areas. Trace metals (e.g., Cu, Cr, Cd, Hg, Pb, and Zn) exhibited a wide range in values throughout the study area. Sediment concentrations of Pb ranged from 32.0 μg Pb g^?1 to 3,630 μg Pb g^?1, Cd from 0.24 μg Cd g^?1 to 4.1 μg Cd g^?1, and Hg from 0.13 μg Hg g^?1 to 9.2 μg Hg g^?1, with generally higher concentrations in either outfall or sewer sediments compared to river bottom-sediments. In the Anacostia River, concentration differences among sewer, outfall, and river sediments, along with downriver spatial trends in trace metals suggest that numerous storm and combined swers are major sources of trace metals. Similar results were observed in both the Tidal Basin and Washington Ship Channel. Cadminum and Pb concentrations are higher in specific sewers and outfalls, whereas the distribution of other metals suggests a more diffuse source to the rivers and basins of the area. Cadmium and Pb also exhibited the greatest enrichment throughout the study area, with peak values located in the Anacostia River, near the Washington Navy Yard. Enrichment factors decrease in the order: Cd>Pb>Zn>Hg>Cu>Cr. Between 70% and 96% of sediment-bound Pb and Cd was released from a N₂-purged IN HCl leach. On average, ≤40% of total sedimentary Cu was liberated, possibly due to the partial attack of organic components of the sediment. Sediments of the tidal freshwater portion of the Potomac estuary reflect a moderate to highly components area with substantial enrichments of sedimentary Pb, Cd, and Zn. The sediment phase that contains these metals indicates the potential mobility of the sediment-bound metals if they are reworked during either storm events or dredging.     

Distribution of trace elements in waters and sediments of the Seversky Donets transboundary watershed (Kharkiv region,Eastern Ukraine)

This paper reports on the aquatic chemistry of trace elements in terms of spatial and temporal distribution, but also pollution sources in the transboundary watershed of the Seversky Donets River (Ukraine/Russia). Bed sediments and filtered water were collected from the Udy and Lopan Rivers at sites from the river source in the Belgorod region (Russia) to rural and urban areas in the Kharkiv region (Ukraine) in May and August 2009. Priority trace elements (As, Cd, Cr, Cu, Hg, Ni, Pb and Zn), an urban tracer (Ag) and additional metals (Co, Mo, V) and Th were measured in stream water and sediments. The low levels and variability of Th-normalized concentrations indicated the absence of geochemical anomalies in the upstream part of the rivers and suggested that these data represent a regional baseline for trace elements in bed sediments. In contrast, water and sediments within the city of Kharkiv were contaminated by Ag, Pb, Cd, Cu, Cr and Zn, which are mainly attributed to municipal wastewater inputs and urban run-off. Results of the environmental quality assessment showed that element concentrations in the sediments can be considered as potentially toxic to aquatic organisms in sites downstream of the wastewater discharges.     

Chromium,chromium isotopes and selected trace elements,western Mojave Desert,USA

Chromium(VI) concentrations in excess of the California Maximum Contaminant Level (MCL) of 50 μg/L occur naturally in alkaline, oxic ground-water in alluvial aquifers in the western Mojave Desert, southern California. The highest concentrations were measured in aquifers eroded from mafic rock, but Cr(VI) as high as 27 μg/L was measured in aquifers eroded from granitic rock. Chromium(VI) concentrations did not exceed 5 μg/L at pH < 7.5 regardless of geology. δ⁵³Cr values in native ground-water ranged from 0.7 to 5.1‰ and values were fractionated relative to the average δ⁵³Cr composition of 0‰ in the earth’s crust. Positive δ⁵³Cr values of 1.2 and 2.3‰ were measured in ground-water recharge areas having low Cr concentrations, consistent with the addition of Cr(VI) that was fractionated on mineral surfaces prior to entering solution. δ⁵³Cr values, although variable, did not consistently increase or decrease with increasing Cr concentrations as ground-water flowed down gradient through more oxic portions of the aquifer. However, increasing δ⁵³Cr values were observed as dissolved O₂ concentrations decreased, and Cr(VI) was reduced to Cr(III), and subsequently removed from solution. As a result, the highest δ⁵³Cr values were measured in water from deep wells, and wells in discharge areas near dry lakes at the downgradient end of long flow paths through alluvial aquifers. δ⁵³Cr values at an industrial site overlying mafic alluvium having high natural background Cr(VI) concentrations ranged from −0.1 to 3.2‰. Near zero δ⁵³Cr values at the site were the result of anthropogenic Cr. However, mixing with native ground-water and fractionation of Cr within the plume increased δ⁵³Cr values at the site. Although δ⁵³Cr was not necessarily diagnostic of anthropogenic Cr, it was possible to identify the extent of anthropogenic Cr at the site on the basis of the δ⁵³Cr values in conjunction with major-ion data, and the δ¹⁸O and δD composition of water from wells.     

Distribution of colloidal trace metals in the San Francisco Bay estuary

The size distribution of trace metals (Al, Ag, Cd, Cu, Fe, Mn, Ni, Sr, and Zn) was examined in surface waters of the San Francisco Bay estuary. Water samples were collected in January 1994 across the whole salinity gradient and fractionated into total dissolved (<0.2 μm colloidal (10 KDa–0.2 μm) and < 10 kDa molecular weight phases. In the low salinity region of the estuary, concentrations of colloidal A1, Ag, and Fe accounted for ≥84% of the total dissolved fraction, and colloidal Cu and Mn accounted for 16–20% of the total. At high salinities, while colloidal Fe was still relatively high (40% of the dissolved), very little colloidal Al, Mn, and Cu (<10%) and no colloidal Ag was detectable. Colloidal Zn accounted for <3% of the total dissolved along the estuary, and colloidal Ni was only detectable (<2%) at the river endmember. All of the total dissolved Cd and Sr throughout the estuary consisted of relatively low molecular weight (<10 kDa) species. The relative affinity of metals for humic substances and their reactivity with particle surfaces appear to determine the amounts of metal associated with colloids. The mixing behavior of metals along the estuary appears to be determined by the relative contribution of the colloidal phase to the total dissolved pool. Metals with a small or undetectable colloidal fraction showed a nonconservative excess (Cd, Cu, Ni, and Mn) or conservative mixing (Sr) in the total dissolved fraction, relative to ideal dilution of river water and seawater along the estuary.

The salt-induced coagulation of colloidal A1, Fe, and Cu is indicated by their highly nonconservative removal along the salinity gradient. However, colloidal metals with low affinity for humic substances (Mn and Zn) showed conservative mixing behavior, indicating that some riverine colloids are not effectively aggregated during their transport to the sea. While colloidal metal concentrations correlated with dissolved organic carbon, they also covaried with colloidal Al, suggesting that colloids are a mixture of organic and inorganic components. Furthermore, the similarity between the colloidal metal:A1 ratios with the crustal ratios indicated that colloids could be the product of weathering processes or particle resuspension. Distribution coefficients for colloidal particles (K_c) and for large, filter-retained particles (K_d) were of the same magnitude, suggesting similar binding strength for the two types of particles. Also, the dependence of the distribution coefficients on the amount of suspended particulate matter (the so-called particle concentration effect) was still evident for the colloids-corrected distribution coefficient (K_p+c) and for metals (e.g., Ni) without affinity for colloidal particles.     

Complex formation and the chemistry of selected trace elements in estuaries

The estuarine chemistry of several metals and anion-forming elements is compared. Differences in the estuarine behaviour of nickel and copper appear to be caused by differences in the stability and reaction rates of organic complexes of these metals. Nickel occurs partially in very stable organic complexes that have an estuarine pathway different from the electrochemically labile (weakly complexed) fraction as the two fractions are not in equilibrium on the estuarine time scale; whereas, the complexes of copper in the estuary are in equilibrium with each other. Titanium occurs largely in a nonlabile form and is subject to removal at low salinities; it is released again at intermediate salinities (25 practical salinity units) and behaves conservatively at higher salinities. Comparison of several anion-forming elements reveals differences; uranium, antimony, and molybdenum show nonconservative behaviour and selenium shows conservative behavior. Voltammetric measurements of the chemical speciation of molybdenum in estuarine waters indicated the unexpected presence of a nonlabile species for this element.     

Mobility of trace elements between the river water,the sediments,and the pore water of Las Catonas Stream,Buenos Aires Province,Argentina

The composition of river water, sediments, and pore waters (down to 30 cm below the bed) of Las Catonas Stream was studied to analyze the distribution of trace elements in a peri-urban site. The Las Catonas Stream is one of the main tributaries of Reconquista River, a highly polluted water course in the Buenos Aires Province, Argentina. The semi-consolidated Quaternary sediments of the Luján Formation are the main source of sediments for Las Catonas Stream. The coarse-grained fraction in the sediments is mainly composed of tosca (calcretes), intraclasts, bone fragments, glass shards, quartz, and aggregates of fine-grained sediments together with considerably amounts of vegetal remains. The clay minerals are illite, illite–smectite, smectite, and kaolinite. For the clay-sized fraction, the external surface area values are mostly between 70 and 110 m²g^?1, although the fraction at 15 cm below the bottom of the river shows a lower surface area of 12 m²g^?1. The N₂ adsorption–desorption isotherms at 77 K for this sample display a behavior indicative of non-porous or macroporous material, whereas the samples above and below present a typical behavior of mesoporous materials with pores between parallel plates (slit-shaped). As, Cr, Cu, and Cd concentrations increase down to 15 cm depth in the sediments, where the highest trace element and total organic carbon (TOC) concentrations were found, and then decrease toward the bottom of the core. Except for As, the levels of the other heavy metals show higher concentration in surficial waters than in pore waters. Distribution coefficients between the sediments, pore water, and surficial water phases indicate that As is released from the sediments to the pore and surficial waters. Cu content strongly correlates with TOC (mainly from vegetal remains), suggesting that this element is mainly bound to the organic phase.