This research focuses on determination of the mineralogical composition, geochemical characteristics and evaluation of pollution status of the Makirina Bay sediments. Calculated enrichment factor ...(EF) values show no enrichment (< 1) for Cd, Ni, and Zn, minor enrichment (< 3) for As, Cu, and Pb, and minor to moderate enrichment for Mo. The results of the sequential leaching procedure for the aforementioned potentially toxic elements (PTE) indicates that the mobility and bioavailability characteristics of the PTE studied declined in the following order: Mo > Cd > Pb > Ni > Zn > Cu > As. Principal component analysis (PCA) and correlation analysis confirmed the PTE distribution depends mainly on the geogenic mineral components and anthropogenic activities in the areas surrounding the bay. Calculated transfer factor (TF) values from sediment to seagrass Cymodocea nodosa (C. nodosa) were < 1, showing that despite the results of the sequential extraction procedure, PTE transfer from sediment to roots was not effective.
The coastal sediment from Makirina Bay in the central Adriatic represents an important source of healing mud (peloid) of high quality organoleptic properties that could in future be used for medical ...treatment. In this study, we estimated the contamination of the sediment with copper which can cause some undesirable health effects. Concentrations of Cu vary from 12 to 63 mg/kg in surface sediment and are higher in the central part of the Bay where the mud fraction prevails. Different normalizing methods were used, i.e. surface/background ratio, index of geoaccumulation, reference metal normalization, enrichment factor (EF) and grain size normalization, to compensate for the influence of the natural variability in sediment mineralogy and granulometry, and to assess whether the concentrations observed in surface sediment represent background or contaminated levels. Results show that Cu concentrations in the surface sediment are twice as high as local background values but in the same range as many clay materials used for medical treatment in Italy. The results also show that more detailed studies on Cu mobility are necessary prior to actual use of peloid in medical treatment.
Due to their balneotherapeutic features, the organic-rich sediments in Makirina Cove are an important source of healing mud. An environmental geochemistry approach using normalization techniques was ...applied to evaluate the anthropogenic contribution of trace metals to sediments used as healing mud. Sediment geochemistry was found to be associated with land-use change and storm events, as well as with proximity of a road with heavy traffic in the summer months. Local valley topography preferentially channels lithogenic and pollutant transport to the cove. Concentrations and distribution of trace metals indicate lithogenic (Ni, Cr, Co) and anthropogenic (Pb, Cu, Zn and Se) contributions to the sediments. The calculation of enrichment factors indicates a moderate (EFs between 2-3.5) input of anthropogenic Cu and Pb in surficial sediments to a depth of 10 cm. Patients using the Makirina Cove sediments as healing mud could be to some extent exposed to enhanced uptake of metals from anthropogenic sources via dermal contact.
The aim of the present study was to determine the concentrations of several potentially toxic elements (PTE) in the recent marine sediment of Makirina bay (central Adriatic), which could according to ...its organoleptic properties be used as a virgin material for medical treatment, wellness and relax purposes. Sediment samples were collected in June and July 2010 from six different sites in the central part of the bay. The range of measured elemental concentrations in analysed surficial sediment were: As (11-15,8 ppm), Cr (61,6 -109,5 ppm), Cu (19,4-54,2 ppm), Pb (16,8-29,6 ppm) and Zn (37-52 ppm). Sediment PTE pollution assessment was performed using contamination factor (CF), contamination degree (Cdeg) and pollution load index (PLI). The calculated environmental index values show a low to moderate contamination status of sediment. Future geochemical investigation on these sediments are necessary prior actual use in various therapeutic treatment.
Background, Aim and Scope Most of the cathment areas supplying water and mineral matter to the Adriatic bays with healing mud/peloids are affected by various degrees of human impact, i.e. activity ...that is introducing various types of contaminants to environment. The bays represent shallow marine depositional environments where organic-rich sediments accumulate. Investigations for balneological characterization of several localities along the Croatian coast have shown that these organic-rich sediments may be classified as healing mud, i.e. peloids. Healing mud due to its balneologic features is in treatment of various diseases and in improvement of the overall health conditions and general well-being. Various components of mud, particularly trace elements, could be absorbed through dermal contact. Therefore, the study of the abundance of such potentially toxic elements as As, Pb, Hg, Cd, Se, Sb, Cu, Zn in marine sediments used as healing mud is necessary in order to know their mobility and to avoid possible intoxications. Methodology In order to assess the most recent record of lithogenic and anthropogenic inputs to the Morinje Bay and Makirina Bay sediments (peloids) on the central Dalmatian coast, concentrations of both lithogenic and potentially toxic element (Cu, Pb, Zn and Mo) concentrations were analysed cores and surface sediments, as well as watershed topsoil. For characterizing the probable anthropogenic effects, the inputs of heavy metals was evaluated by calculation of enrichment factors (EF) for these elements, using Sc as the conservative element. Mobility of metals was assessed by application of the first step (0.11 mol dm-³ CH₃COOH) of the harmonized BCR three-step sequential extraction procedure. Results Analysis of ten composite toposil samples from the vineyards (5 sampling sites) and uncultivated slopes (5 sampling sites) were used to determine concentrations of metals in soils from the watershed. The Cu concentrations in the vineyard soils ranged from 105 to 553 mg/kg. Analyses of soils with visible traces of the Bordeaux mixture showed that Pb (Pb/Sc 5.6) and Zn (Zn/Sc 21.5) were also being added to the soil. The amount of Cu bound to the carbonate phase of composite vineyard soil was 53.6 mg/kg or 22% of total Cu, while soil containing the Bordeaux mixture contained 2,827 mg/kg of extractable Cu (70% of total Cu), thus indicating that copper is probably supplied to the bay not only with eroded soil but also in runoff solution. Morinje Bay sediments have a higher mean Cu concentration (71.4 mg/kg) than the surrounding soils on limestone (which are not arable) and lower than the soils developed on flysch bedrock (arable soils). In the sediment cores from Morinje Bay, Mo increased (from 4.5 to 43 mg/kg) with increasing depth. The Cu EF in the surface sediments of Makirina Bay fluctuates around 2.5 in the offshore direction and drops to below 2 in the most distant profile. Discussion The calculated enrichment factors or Cu and Pb in sediments of the two bays show that lead is accumulating in the smaller Makirina Bay as a consequence of road runoff which drained into the bay. Copper, on the other hand, is the major indicator of anthropogenic load in the larger Morinje Bay watershed with extensive vineyard activity. Comparisons of total concentrations of the Zn, Pb, and Cu in sediments from both bays shows that they are below PEL for these elements. However, the high accumulation rate of sediment with bio-available Cu could reach levels in Morinje Bay which could cause toxic effects. High amounts of extractable Cu (11-13%) are present in the top 20 cm of the sediment core, which corresponds to the highest Cu enrichment factors (from 2.3 to 4.3). The sediment from the deeper part of the core (75-80 cm) contains only 2.8% of extractable Cu. The anomalous accumulation of Mo in deeper parts of the cores is probably a result of a natural process caused by resolubilization of Mo under aerobic conditions, i.e. upon air-drying of the sediments due to tidal conditions in Morinje Bay. Conclusions The geochemical analyses were performed to evaluate the extent of the anthropogenic contribution from the two major sources of potentially toxic elements to their lithogenic fraction in the sediments. The results for Cu, Pb Zn imply that they have distinct distributions, which imply anthropogenic burdening of the sediments/peloids while Mo is enriched due to natural processes. Since the analysed sediments are topically used as healing mud for various rheumatic diseases, the contents of bioavailable metals is important since heavy metals act directly or indirectly on intercellular proteins in the skin. The results of chemical characterization of heavy metals show that both the calculation of enrichment factors and extraction analysis can identify anthropogenic contribution of heavy metals to the sediment. Contaminants released into coastal environments can limit the use of these sediments for therapeutic purposes and as indicator thresholds. Recommendations and Perspectives Along the eastern Adriatic coast, sediments deposited in shallow bays have frequently been used for balneotherapy, a procedure dating back to Roman times. Due to the high expansion of wellness tourism in Croatia, a demand for healing mud has risen dramatically, leading to both uncontrolled exploitation of sediments and unsupervised application by individuals. Therefore, the results of this study, are intended to be used as an argument for local environmental authorities to plan use of sediments for healing/wellness purposes from bays with watersheds without anthropogenic influence. Also, there is a necessity to determine probable effects levels for bioavailable (mobile) metals and other potentially toxic substances that can enter the human body through the skin. The levels should be defined for both total and extractable levels of elements if the sediments are to be used as healing mud.
Makirina Cove was formed by the Holocene sea-level rise whichcaused a marine ingression into the depression formed within Albian–Cenomanian dolomites at approximately 4.5 ka B.P. At present, ...MakirinaCove represents an restricted, stressed, shallow-marine (<2 m)ecosystem characterized by varying seawater temperatures (0–35°C)as well as fluctuating salinities (up to 41‰) affected by seasonallyenhanced evaporation, continuous freshwater supply through on-shoreand submarine springs associated with the coastal karst area and surface run-off episodes. These environmental conditions have beenconducive to high primary production of organic matter resulting inthe formation of organic-rich deposits which contain up to 5 wt.% oforganic carbon. Up to the present times, 3.5 m of sediments have beendeposited indicating a relatively high sedimentation rate estimated at0.75 m/1.0 ka in the northern central part of the Cove.The sediments are being deposited mostly as poorly sortedclayey–sandy silts. The distribution and concentration of most of thechemical elements is dependant on the mineralogical composition andgranulometric features of the Makirina sediments, which show valuesmore or less similar to those from the Central Adriatic. Accordingly,there is a positive correlation with Al and K concentrations increasingoff-shore and with the depth being associated with increasing concentrations of clay minerals within the clay fraction. The same holdstrue for concentrations of some trace elements, especially Mo and Sewhich is consistent with the distribution pattern of sulphides.Selenium is preferentially enriched in authigenic pyrite and itis probably the major source of Se in the Makirina Cove sediments.The concentrations of Ca, Mg and Sr decrease off-shore and they arelinked to the composition of the surrounding carbonate rocks. Thesaturation indices show that the water is supersaturated with respectto carbonates enabling the precipitation of authigenic amorphous orcrystalline carbonate phases from the pore water in the upper segmentof the sediment column. According to the oxygen isotopic (δ18O) composition,molluscs precipitated their carbonate shells mostly duringwarmer periods (May to November) at or near isotopic equilibriumwith their ambient waters. The carbon isotopic δ13C composition ofmollusc carbonate shells is environmentally affected due to oxidationand decomposition of organic matter as well as influxes of fresh waterinto the Cove, indicating their formation out of the predicted isotopicequilibrium with atmospheric CO2. Palynological and organic carbonisotopic (δ13C) composition shows that the sedimentary organic matter(SOM) is 70–90% lipid- and hydrogen-rich and on average 2/3 marinederived (mainly phytoplankton, bacteria and marine macrophytes) and1/3 terrestrially derived (mainly woody tissue). The variations in composition of SOM have been noted as a function of the distance fromthe shore. The type and the preservation state of SOM and pyrite aswell as the measurements of Eh, pH, total alkalinity, dissolved inorganiccarbon (DIC) and the enrichment of redox-sensitive trace elements,indicate oxygen-depleted depositional conditions and that thesediment is highly reductive even in the uppermost segment at thesediment/water interface. According to the results obtained from theapplied methods, the features of Makirina sediments strongly reflectthe given depositional conditions within this restricted, stressed, shallow-marine environment where these organic-rich sediments originate,and may therefore serve as a calibration standard in further investigations
Makirina Cove was formed by the Holocene sea-level rise which caused a marine ingression into the depression formed within Albian–Cenomanian dolomites at approximately 4.5 ka B.P. At present, ...Makirina Cove represents an restricted, stressed, shallow-marine (<2m) ecosystem characterized by varying seawater temperatures (0–35°C) as well as fluctuating salinities (up to 41‰) affected by seasonally enhanced evaporation, continuous freshwater supply through on-shore and submarine springs associated with the coastal karst area and surface run-off episodes. These environmental conditions have been conducive to high primary production of organic matter resulting in the formation of organic-rich deposits which contain up to 5 wt.% of organic carbon. Up to the present times, 3.5 m of sediments have been deposited indicating a relatively high sedimentation rate estimated at 0.75 m/1.0 ka in the northern central part of the Cove.The sediments are being deposited mostly as poorly sorted clayey–sandy silts. The distribution and concentration of most of the chemical elements is dependant on the mineralogical composition and granulometric features of the Makirina sediments, which show values more or less similar to those from the Central Adriatic. Accordingly, there is a positive correlation with Al and K concentrations increasing off-shore and with the depth being associated with increasing concentrations of clay minerals within the clay fraction. The same holds true for concentrations of some trace elements, especially Mo and Se which is consistent with the distribution pattern of sulphides.Selenium is preferentially enriched in authigenic pyrite and it is probably the major source of Se in the Makirina Cove sediments. The concentrations of Ca, Mg and Sr decrease off-shore and they are linked to the composition of the surrounding carbonate rocks. The saturation indices show that the water is supersaturated with respect to carbonates enabling the precipitation of authigenic amorphous or crystalline carbonate phases from the pore water in the upper segment of the sediment column. According to the oxygen isotopic (δ18O) composition, molluscs precipitated their carbonate shells mostly during warmer periods (May to November) at or near isotopic equilibrium with their ambient waters. The carbon isotopic δ13C composition of mollusc carbonate shells is environmentally affected due to oxidation and decomposition of organic matter as well as influxes of fresh water into the Cove, indicating their formation out of the predicted isotopic equilibrium with atmospheric CO2. Palynological and organic carbon isotopic (δ13C) composition shows that the sedimentary organic matter (SOM) is 70–90% lipid- and hydrogen-rich and on average 2/3 marine derived (mainly phytoplankton, bacteria and marine macrophytes) and 1/3 terrestrially derived (mainly woody tissue). The variations in composition of SOM have been noted as a function of the distance from the shore. The type and the preservation state of SOM and pyrite as well as the measurements of Eh, pH, total alkalinity, dissolved inorganic carbon (DIC) and the enrichment of redox-sensitive trace elements, indicate oxygen-depleted depositional conditions and that the sediment is highly reductive even in the uppermost segment at the sediment/water interface. According to the results obtained from the applied methods, the features of Makirina sediments strongly reflect the given depositional conditions within this restricted, stressed, shallow-marine environment where these organic-rich sediments originate, and may therefore serve as a calibration standard in further investigations.
Makirina Cove was formed by the Holocene sea-level rise which caused a marine ingression into the depression formed within Albian–Cenomanian dolomites at approximately 4.5 ka B.P. At present, ...Makirina Cove represents an restricted, stressed, shallow-marine (<2m) ecosystem characterized by varying seawater temperatures (0–35°C) as well as fluctuating salinities (up to 41‰) affected by seasonally enhanced evaporation, continuous freshwater supply through on-shore and submarine springs associated with the coastal karst area and surface run-off episodes. These environmental conditions have been conducive to high primary production of organic matter resulting in the formation of organic-rich deposits which contain up to 5 wt.% of organic carbon. Up to the present times, 3.5 m of sediments have been deposited indicating a relatively high sedimentation rate estimated at 0.75 m/1.0 ka in the northern central part of the Cove.
The sediments are being deposited mostly as poorly sorted clayey–sandy silts. The distribution and concentration of most of the chemical elements is dependant on the mineralogical composition and granulometric features of the Makirina sediments, which show values more or less similar to those from the Central Adriatic. Accordingly, there is a positive correlation with Al and K concentrations increasing off-shore and with the depth being associated with increasing concentrations of clay minerals within the clay fraction. The same holds true for concentrations of some trace elements, especially Mo and Se which is consistent with the distribution pattern of sulphides.
Selenium is preferentially enriched in authigenic pyrite and it is probably the major source of Se in the Makirina Cove sediments. The concentrations of Ca, Mg and Sr decrease off-shore and they are linked to the composition of the surrounding carbonate rocks. The saturation indices show that the water is supersaturated with respect to carbonates enabling the precipitation of authigenic amorphous or crystalline carbonate phases from the pore water in the upper segment of the sediment column. According to the oxygen isotopic (δ18O) composition, molluscs precipitated their carbonate shells mostly during warmer periods (May to November) at or near isotopic equilibrium with their ambient waters. The carbon isotopic δ13C composition of mollusc carbonate shells is environmentally affected due to oxidation and decomposition of organic matter as well as influxes of fresh water into the Cove, indicating their formation out of the predicted isotopic equilibrium with atmospheric CO2. Palynological and organic carbon isotopic (δ13C) composition shows that the sedimentary organic matter (SOM) is 70–90% lipid- and hydrogen-rich and on average 2/3 marine derived (mainly phytoplankton, bacteria and marine macrophytes) and 1/3 terrestrially derived (mainly woody tissue). The variations in composition of SOM have been noted as a function of the distance from the shore. The type and the preservation state of SOM and pyrite as well as the measurements of Eh, pH, total alkalinity, dissolved inorganic carbon (DIC) and the enrichment of redox-sensitive trace elements, indicate oxygen-depleted depositional conditions and that the sediment is highly reductive even in the uppermost segment at the sediment/water interface. According to the results obtained from the applied methods, the features of Makirina sediments strongly reflect the given depositional conditions within this restricted, stressed, shallow-marine environment where these organic-rich sediments originate, and may therefore serve as a calibration standard in further investigations.
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