Physico-chemical characteristics of the peloid mud from Morinje Bay (eastern Adriatic coast, Croatia): suitability for use in balneotherapy

The study conducted in the Morinje Bay (Central Dalmatia, Croatia) included the investigation of the sedimentological, physico-chemical and geochemical properties of the Morinje Bay sediments in order to assess the suitability of the material for wellness-related purposes including medicinal use. The sedimentological characteristics of the Morinje mud are in accordance with the geological origin of the material; the sediment is fine grained, composed mostly of carbonates, quartz and clay minerals. The composition of the sediment determines the physico-chemical properties of the mud. The high content of carbonate minerals diminishes adsorbing the characteristics of the mud to some extent; however, they are still comparable to some commercial mud already successfully used for medicinal purposes. Geochemical analyses have shown that trace metals concentrations in the Morinje Bay samples were mostly in the range with similar material from unpolluted Adriatic environments. Only the concentrations of Cu, Pb, Zn and As were slightly higher than in the reference material, but still within acceptable limits.     

Residuary Toxic Elements And PAHs in Sediments of the Zbiornik Gilow Tailings Pond and Zimmica Stream from Lubin District, Southwest Poland

Eight selected elements (As, Cd, Co, Cu, Pb, Zn, Cr and Ni) were determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES) in five samples from the tailings pond (Zbiornik Gilow) and waste water stream (Zimmica) in the Kupferschiefer mining district in Southwest Poland. Waste water from mining and concentration plants was discharged into Zbiornik Gilow pond for 30 years before 1989. Below Zbiornik Gilow the water flows through Zimmica stream, and then discharges into the River Odra. The analytic results indicate that the contamination of As, Cd, Co, Cu, Pb and Zn has spread out over 5km, and the contamination by Ni and Cr extends for 1.5km along the Zimmica stream although the stream has been abandoned since 1989. These elements could still be toxic for plants, animals and humans. Polycyclic aromatic hydrocarbons (PAHs) were determined by GC and GC/MS. The results of the sediment samples show a contamination of PAHs only in trace contents.     

Distribution of selected elements and PAH in freshly deposited sediments of waste water streams from Lubin district, Southwest Poland

Nine selected elements (Cu, Pb, As, Zn, Co, Ni, Cr, Cd and Fe) were determined by inductively coupled plasma atomic emission spectroscopy in 15 samples from the tailings pond (Zelazny Most) and waste water streams (Moskorzynke and Rudna) in the Kupferschiefer mining district in Southwest Poland. Waste water from mining and industry enter the Zelazny Most pond. The water then flows through Moskorzynke and Rudna streams, and discharges into the River Odra. The analytic results indicate that the contamination with Cu, Pb, Zn, As, Co, Cd and Fe extend about 6km along the streams in contrast to the nonpolluted samples close the River Odra. Their concentrations reach a level, which could be toxic for plants, animals and humans. The contamination with Ni and Cr continued at least 20km along Rudna stream. Besides mechanical transport, redox conditions and C_org contents also played an important role for trace element and Fe contamination in Rudna stream. The samples with high C_org contents have also high contents of trace metals. In Moskorzynke stream the element contamination was mainly caused by mechanical transport of particles. Polyaromatic hydrocarbon (PAH), which is abundant in Kupferschiefer, is toxic for animals and humans. The PAH concentration in the stream sediments was determined by GC and GC/MS. The results indicate that the contamination of PAH reaches 6 and 17mgkg_–1 in samples TP1 and RS6, respectively. In the other samples, the PAH contents are lower than 3mgkg_–1. Some PAH could be solved by waste water in the tailings pond and migrated to the stream sediments. Some PAH might be contained in particles which were transported mechanically from the tailings pond into stream sediments.     

Association of minor and trace elements with mineralogical constituents of urinary stones: A hard nut to crack in existing studies of urolithiasis

The role of metals in urinary stone formation has already been studied in several publications. Moreover, urinary calculi can also be used for assessing exposure of humans to minor and trace elements in addition to other biological matrices, for example, blood, urine, or hair. However, using urinary calculi for biomonitoring of trace elements is limited by the association of elements with certain types of minerals. In this work, 614 samples of urinary calculi were subjected to mineralogical and elemental analysis. Inductively coupled plasma mass spectrometry and thermo-oxidation cold vapor atomic absorption spectrometry were used for the determination of major, minor, and trace elements. Infrared spectroscopy was used for mineralogical analysis, and additionally, it was also employed in the calculation of mineralogical composition, based on quantification of major elements and stoichiometry. Results demonstrate the applicability of such an approach in investigating associations of minor and trace elements with mineralogical constituents of stones, especially in low concentrations, where traditional methods of mineralogical analysis are not capable of quantifying mineral content reliably. The main result of this study is the confirmation of association of several elements with struvite (K, Rb) and with calcium phosphate minerals, here calculated as hydroxylapatite (Na, Zn, Sr, Ba, Pb). Phosphates were proved as the most important metal-bearing minerals in urinary calculi. Moreover, a significantly different content was also observed for Fe, Zr, Mo, Cu, Cd, Se, Sn, and Hg in investigated groups of minerals. Examination of such associations is essential, and critical analysis of mineral constituents should precede any comparison of element content among various groups of samples.     

The Role of Suspended Matter in Assessing the Assimilative Capacity Case Study of Two Estuaries in the Adriatic Sea

Suspended particulate matter has been studied in two Adriatic river mouths to assess its role as a transport vehicle for waste disposal into the Adriatic sea.

The larger of the two, the Adige River (northwestern Adriatic coast, Italy), carries large quantities of solids and builds up a prodelta. the Krka River (eastern Adriatic coast, Croatia, Yugoslavia) is a typical karst river, and carries small quantities of suspended matter, since it drains carbonate terrains.

The resulting disposal of contaminants into the Adriatic sea is largely governed by the adsorption/desorption processes occurring in the estuarine mixing region. Surface adsorption properties, the specific surface area, and the nature and reactivity of the organic film coating determine the partitioning of pollutants between the dissolved and particulate state.

The observations reported point to the key role of particulates in transport of pollutants from land to sea. the concept of the assimilative capacity of the estuarine area requires detailed scientific knowledge on the geochemical behaviour of particulates.

In the Adige River mouth, lead, chromium, zinc, and nickel are accumulated in the prodelta sediments, and thus the loading of the sea with these metals is diminished, whereas in the Krka River estuary, desorption and mobilization of some trace metals occurs.     

Seasonal variation and partition of trace metals (Fe, Zn, Cu, Mn, Cr, Cd and Pb) in surface sediments: relationship with physico-chemical variables of water from the Calabar River, South Eastern Nigeria

The seasonal variation and partition of trace metals (Fe, Cu, Zn, Mn, Cd, Cr and Pb) in the surface sediments of the Calabar River are reported. Chemical partition of the metals in the sediments reveals that 2–30% of the total metal load was contributed by the non-detrital (acid-soluble) fraction, while fine-grained host minerals/compounds are the main carriers of the detrital (acid-insoluble) fraction (70–98%). Using multivariate statistical analysis, the seasonal fluctuations in the distribution of some of the metals show significant influence by physio-chemical changes (dissolved oxygen, pH, salinity and conductivity) in the water column. Fe–Mn oxide grain coatings and sulphide materials have been identified as scavengers of some of the non-detrital and detrital trace metals in the sediments. On the basis of index of geoaccumulation (I-geo) and comparison with previous studies, the Calabar River surface sediments have been classified as unpolluted.     

Trace elements distributions at Datoko-Shega artisanal mining site,northern Ghana

Environmental geochemistry classifies elements into essential, non-essential and toxic elements in relationship to human health. To assess the environmental impact of mining at Datoko-Shega area, the distributions and concentrations of trace elements in stream sediments and soil samples were carried out. X-ray fluorescence analytical technique was used to measure the major and trace element concentrations in sediments and modified fire assay absorption spectrometry in soils. The results showed general depletion of major elements except titanium oxide (TiO₂) compared to the average crustal concentrations. The retention of TiO₂ at the near surface environment probably was due to the intense tropical weathering accompanied by the removal of fine sediments and soil fractions during the harmattan season by the dry north-east trade winds and sheet wash deposits formed after flash floods. The results also showed extreme contamination of selenium (Se), cadmium (Cd) and mercury (Hg), plus strong contaminations of arsenic (As) and chromium (Cr) in addition to moderate contamination of lead (Pb) in the trace element samples relative to crustal averages in the upper continental crust. However Hg, Pb and Cd concentrations tend to be high around the artisanal workings. It was recognised from the analysis of the results that the artisanal mining activity harnessed and introduces some potentially toxic elements such as Hg, Cd and Pb mostly in the artisan mine sites. But the interpretation of the trace element data thus invalidates the elevation of As concentrations to be from the mine operations. It consequently noticed As values in the mine-impacted areas to be similar or sometimes lower than As values in areas outside the mine sites from the stream sediment results.

     

Chemistry, mineralogy and radioactivity in posidonia oceanica meadows from North-Western Sicily

This paper presents measurements of major, minor, metal trace elements and radionuclides in sediments and in Posidonia oceanica samples from north-western Sicily (Italy). The mineralogical and chemical composition of sediments were determined by X-ray diffraction and X-ray fluorescence techniques, respectively. A flame atomic absorption spectrophotometry was used to measure concentrations of Cu, Zn, Cd and Pb in P. oceanica samples and in sediments. Specific activities of selected radionuclides have been determined by high-resolution gamma spectrometry. Standard statistical analysis was used to assess correlations between different elements and different sample types.     

Chemistry,mineralogy and radioactivity in posidonia oceanica meadows from North-Western Sicily

This paper presents measurements of major, minor, metal trace elements and radionuclides in sediments and in Posidonia oceanica samples from north-western Sicily (Italy). The mineralogical and chemical composition of sediments were determined by X-ray diffraction and X-ray fluorescence techniques, respectively. A flame atomic absorption spectrophotometry was used to measure concentrations of Cu, Zn, Cd and Pb in P. oceanica samples and in sediments. Specific activities of selected radionuclides have been determined by high-resolution gamma spectrometry. Standard statistical analysis was used to assess correlations between different elements and different sample types.     

Heavy metal contamination in the Tanat Valley,North Wales

The Tanat Valley area of North Powys, Wales, has a long history of metalliferous mining, the most active period of extraction being during the 18th century, while the largest mine, Llangynog, was in production until 1899. Ore minerals found in the area include galena (PbS), sphalerite (ZnS) and chalcopyrite (CuFeS2). Below the Llangynog mine the valley is heavily contaminated with elevated levels of Pb, Zn, Cu and Cd in soils and river sediments. On the valley floor subsoil metal levels frequently greatly exceed those of topsoils which probably reflects contamination of the floodplain during the peak period of mining. High levels of base metals in the stream sediments some 2 km downstream of the mine area are thought to be due to river erosion of the contaminated bank material. Contamination derived from the old mine tips results in extremely high levels of heavy metals in soils and stream sediments in the immediate vicinty of the old workings. Some metal contamination is also thought to derive from previously undetected mineralisation.     

Geochemical forms of trace metals in mangrove sediments—Red Sea (Egypt)

Seven sediment samples from mangrove sediments of the Red Sea were taken in order to evaluate the possible contamination of the sediments by trace metals (iron (Fe), manganese (Mn), zinc (Zn), copper (Cu), lead (Pb) and cadmium (Cd)). Sequential extraction techniques were performed to study the different geochemical forms of these metals. X-ray diffraction analysis has been performed to correlate the mineralogical composition with the geochemical forms of the studied elements. The results of Fe and Mn contents indicate that they are in large part from lithogenous origin. The elevated concentrations are associated with the residual form ranged from 70 to 93% for Fe and 46 to 70% for Mn. The percentage of Zn, Cu, Cd and Pb in the non-residual form was much greater than that of the residual fractions. This reflects the high mobility and bioavailability of these metals in mangrove sediments of the Red Sea. X-ray diffraction analysis revealed the presence of silicate components including quartz, feldspars and clay minerals in some locality. Non-silicate components recorded in the study area as calcite as well as, Mg-calcite. Quantitatively both components i.e. silicate and carbonate varied according to their source material.     

Geochemical forms of trace metals in mangrove sediments—Red Sea (Egypt)

Seven sediment samples from mangrove sediments of the Red Sea were taken in order to evaluate the possible contamination of the sediments by trace metals (iron (Fe), manganese (Mn), zinc (Zn), copper (Cu), lead (Pb) and cadmium (Cd)). Sequential extraction techniques were performed to study the different geochemical forms of these metals. X-ray diffraction analysis has been performed to correlate the mineralogical composition with the geochemical forms of the studied elements. The results of Fe and Mn contents indicate that they are in large part from lithogenous origin. The elevated concentrations are associated with the residual form ranged from 70 to 93% for Fe and 46 to 70% for Mn. The percentage of Zn, Cu, Cd and Pb in the non-residual form was much greater than that of the residual fractions. This reflects the high mobility and bioavailability of these metals in mangrove sediments of the Red Sea. X-ray diffraction analysis revealed the presence of silicate components including quartz, feldspars and clay minerals in some locality. Non-silicate components recorded in the study area as calcite as well as, Mg-calcite. Quantitatively both components i.e. silicate and carbonate varied according to their source material.     

Heavy metals in surface water and stream sediments in Jamaica

The levels of heavy metals in water and stream sediments in Jamaica are presented and compared to levels in soils and environmental standards. Heavy metals (cadmium, chromium, copper, mercury, nickel, lead and zinc) appear to be less of a problem to Jamaica's freshwater environment than might be expected given the concentrations in soils. This can be explained by taking into account the dynamics of the Jamaican water environment and the relative absence of anthropogenic sources. The dynamics of the freshwater system on the other hand, could pass any environmental threat to the coastal environment. Because the stream sediments are relatively coarse and contain little organic material the bio-availability of micropollutants such as heavy metals from the sediments can be expected to be relatively high.     

Ameliorants to immobilize Cd in rice paddy soils contaminated by abandoned metal mines in Korea

The Yarlung Tsangbo (YT) is a large river running across southern Tibet and has significant effects on its lower reaches, the Ganges–Brahmaputra Basin. In order to investigate the geochemical features of the YT, 18 surface sediment samples were collected; ten trace element concentrations were measured for bulk sediments and two fine grain size fractions. Meanwhile, basic physicochemical parameters and element concentrations of river water were also analyzed. Results indicated that the river water was alkaline (pH 8.42) and that dissolved oxygen was mainly controlled by river water temperature. Some elements (e.g., Zn and Ni) showed close negative relationship to mean grain size of the sediments. Concentrations of most heavy metals, except As of the YT bulk sediments, were similar to those of Upper Crustal Concentration and its lower reaches, indicating almost no anthropogenic impact. Arsenic of the YT sediments was derived fundamentally from the parent rocks of the YT Basin and was far higher than that of its lower reaches. This indicates that relatively small amounts of As from the study area were transported down to the Brahmaputra River under present, relatively dry climatic conditions. However, more YT sediments might have been transported to its low reaches during the Holocene due to the wet climate, giving high As concentration in Holocene sediments of the Ganges–Brahmaputra Basin. Thus, As transported by the YT may produce important influence on the Ganges–Brahmaputra Basin and contribute to its high As concentration in groundwater.     

Heavy Metal Pollution in Sediment from the Eastern Adriatic Coast,Croatia

Abstract

Sediment samples were collected from the Adriatic Sea in areas near large coastal towns along the eastern Adriatic coast (Zadar, [Ncirc]ibenik, Split, Plo?e and Dubrovnik).

Considerable quantities of untreated effluents are discharged via freshwater runoff and a variety of industrial waste waters, significantly affecting the quality of marine sediments.

Distribution of some trace metals (Pb, Cu, Ni, Cr, Zn, Mn, Cd, and Al) involved in problems related to metal pollution in Adriatic sediment were examined. Values are expressed as a total concentration of heavy metals of sediment dry weight.

Spatial distribution of some trace metal values in sediments and correlation of results for grain size effect were examined. the trace elements in marine sediments generally remain in the fine grained fraction, often in the silt-clay fraction. Higher values of heavy metals in some areas (Split, Sibenik) could be attributed to anthropogenic effects, i.e. to land-based activities. the main cause of higher values of some metals at open sea sites and in some coastal areas are probably caused naturally by sedimentation processes in those areas. Our results show that the sediments undoubtedly play a key role in determining the transport and ultimate fate of contaminants.     

Heavy Metals in the Bed and Suspended Sediments of Anyang River, Korea: Implications for Water Quality

The objective of this study is to compare Anyang River bed sediments with water chemical composition and to assess the anthropogenic chemical inputs into the river system. Eight sampling locations were chosen along the river channel. Bed and suspended river sediments and water samples were collected, and analyzed for their chemical and physical composition. Data revealed that trace element concentrations in the river water were generally below world average, except for As, Mn, Ni and Cr. Among the three phases: water, bed and suspended sediment, more than 99% of the trace elements was associated with the bed sediment. Concentrations of trace elements in the sediment were a function a particle size distribution and organic content. The calculated degrees of enrichment based on the least influenced sample (ASD 1) indicated the river sediments were enriched with respect to background. The enrichment factors for Pb, Zn and As were relatively lower than for Cr, Co, Ni and Zn. The difference in the enrichment seems to reflect the human activities influence in the basin, and specially for Cd. Speciation of the elements in the five different chemical forms in the sediment by sequential extraction indicated that the reducible fraction was predominant for Fe, Zinc and Cu showed an irregular variation among the different fractions; whereas, Cd and Pb were more regular. Zinc and Cu highly existed mostly in exchangeable forms. Acid soluble and reducible forms were also important for most metals. The speciation implies that the metals associated with the sediment are subject to release into water bodies as goechemical variables (pH and Eh) change. Currently, the introduced metals are deposited near the source area and are mostly associated with the sediment, implying that the river bed sediment acts mainly as a sink, rather than a pool. The accumulated and enriched toxic trace elements can pose a potential pollution of river water.     

Environmental impact of historical harbour city Zadar (Croatia) on the composition of marine sediments and soils

Sediment samples and soils along the coast line of the Adriatic Sea were sampled along a transect near the coast line at Zadar/Croatia, ranging from north-western suburbs via the historical centre and the industrial area to south-east suburbs. The sediments were dominated by carbonates and clay minerals, and contaminations with Cd-Cu-Pb-Zn-TOC (total organic carbon) at the historical centre and the industrial site were detected, as well as P and Mo input at the mouth of a small creek, probably from agriculture. No trends between the composition of surface and subsurface sea sediments were seen. At the historic harbour site, total element concentrations versus grain size showed a minimum in the fine silt fraction for most of the elements analysed. The soil samples behind the shoreline were not carbonaceous, but dominated by Fe-Al- oxides, some contained high levels of Be-Cd-Cu-Sn-Zn. Surprisingly, high TOC values within the soils might be assigned to human impacts, not to humus. Contrary to data from street dust samples from Seoul city/Korea, which were measured within our laboratory at the same time, Pt-Ir-Au were at ambient levels due to the limited use of catalysts in cars in the Zadar area at the time of sampling.     

Arsenic partitioning among particle-size fractions of mine wastes and stream sediments from cinnabar mining districts

Tailings from abandoned mercury mines represent an important pollution source by metals and metalloids. Mercury mining in Asturias (north-western Spain) has been carried out since Roman times until the 1970s. Specific and non-specific arsenic minerals are present in the paragenesis of the Hg ore deposit. As a result of intensive mining operations, waste materials contain high concentrations of As, which can be geochemically dispersed throughout surrounding areas. Arsenic accumulation, mobility and availability in soils and sediments are strongly affected by the association of As with solid phases and granular size composition. The objective of this study was to examine phase associations of As in the fine grain size subsamples of mine wastes (La Soterraña mine site) and stream sediments heavily affected by acid mine drainage (Los Rueldos mine site). An arsenic-selective sequential procedure, which categorizes As content into seven phase associations, was applied. In spite of a higher As accumulation in the finest particle-size subsamples, As fractionation did not seem to depend on grain size since similar distribution profiles were obtained for the studied granulometric fractions. The presence of As was relatively low in the most mobile forms in both sites. As was predominantly linked to short-range ordered Fe oxyhydroxides, coprecipitated with Fe and partially with Al oxyhydroxides and associated with structural material in mine waste samples. As incorporated into short-range ordered Fe oxyhydroxides was the predominant fraction at sediment samples, representing more than 80 % of total As.     

Environmental impact of historical harbour city Zadar (Croatia) on the composition of marine sediments and soils

Sediment samples and soils along the coast line of the Adriatic Sea were sampled along a transect near the coast line at Zadar/Croatia, ranging from north-western suburbs via the historical centre and the industrial area to south-east suburbs. The sediments were dominated by carbonates and clay minerals, and contaminations with Cd–Cu–Pb–Zn–TOC (total organic carbon) at the historical centre and the industrial site were detected, as well as P and Mo input at the mouth of a small creek, probably from agriculture. No trends between the composition of surface and subsurface sea sediments were seen. At the historic harbour site, total element concentrations versus grain size showed a minimum in the fine silt fraction for most of the elements analysed. The soil samples behind the shoreline were not carbonaceous, but dominated by Fe–Al– oxides, some contained high levels of Be–Cd–Cu–Sn–Zn. Surprisingly, high TOC values within the soils might be assigned to human impacts, not to humus. Contrary to data from street dust samples from Seoul city/Korea, which were measured within our laboratory at the same time, Pt–Ir–Au were at ambient levels due to the limited use of catalysts in cars in the Zadar area at the time of sampling.     

Elemental Analysis of Water and Sediments By External Beam Pixe Part 4. Aliakmon River, Greece

The Aliakmon River originates in the North Western part of Greece, traverses the Western part of Macedonia, and discharges into the Thermaikos Bay in the North Aegean Sea. Proton induced X-ray emission (PIXE) method with external beam was used for the determination of the metallic elements in the waters and sediments of the Aliakmon River. the pH, dissolved oxygen, conductivity, and total phosphate and nitrate concentrations were also monitored in the water samples. Data collected for a 20-month period indicate that the Aliakmon River can be still considered as an unpolluted river.