Goran Kniewald

137Cs baseline levels in the Mediterranean and Black Sea: A cross-basin survey of the CIESM Mediterranean Mussel Watch programme

The common mussel Mytilus galloprovincialis was selected as unique biomonitor species to implement a regional monitoring programme, the CIESM Mediterranean Mussel Watch (MMW), in the Mediterranean and Black Seas. As of today, and upon standardization of the methodological approach, the MMW Network has been able to quantify (137)Cs levels in mussels from 60 coastal stations and to produce the first distribution map of this artificial radionuclide at the scale of the entire Mediterranean and Black Seas. While measured (137)Cs levels were found to be very low (usually < 1 Bq kg(-1) wet wt) (137)Cs activity concentrations in the Black Sea and North Aegean Sea were up to two orders of magnitude higher than those in the western Mediterranean Basin. Such effects, far from representing a threat to human populations or the environment, reflect a persistent signature of the Chernobyl fallout in this area.

Organotin compounds in seawater and Mytilus galloprovincialis mussels along the Croatian Adriatic Coast.

In this work, data on the level of organotin compounds (OTCs) in seawater and mussels collected along the entire Croatian Adriatic Coast are presented. The samples were collected in 2009 and 2010 at 48 locations representing different levels of maritime activities, including marinas, ports and reference sites. Butyltins (BuTs) were found in all analyzed samples, representing >97% of OTCs, and ranged from 0.46 to 27.98 ng Sn L(-1) in seawater and from <6 to 1675 ng Sn g(-1) in mussels. The results indicate a recent input of TBT, with the highest concentrations of BuTs found in the marinas. It appears that the Adriatic coast is still polluted with TBT despite the fact that TBT-containing antifouling paints have been banned in Croatia since 2008. It is questionable how much TBT pollution decreased since 2005, when a high incidence of imposex was established in the same area.

Monitoring of total metal concentration in sludge samples: case study for the mechanical-biological wastewater treatment plant in Velika Gorica, Croatia.

In this paper, monitoring of total metal concentration in sludge samples from wastewater treatment process is elaborated. The presented results summarize the analyses of sludge samples in a period from 2008 to 2012. Possible sources of pollutions are given. Primarily, waste solid samples were collected from different pretreatment steps: (A) coarse grid, (B) fine grid and (C) aerated sand grease grid. Samples of A and B followed a repeatable pattern in 2008 and 2010. According to the results from 2008, samples of C contained measurable concentration of the following metals (mg/kg dry matter): Zn (21), Ni (1.05) and Ba (14.9). Several types of sludge samples were analyzed: fresh raw sludge (PS; 6-12 hour old), the sludge from the digester for anaerobic sludge treatment (DS; 48-72 hour old), samples from lagoons where the sludge is temporarily deposited (DOS and DOSold; 30-120 days) and sludge samples from agricultural areas (AA; aged over 180 days). Additionally, samples of dehydrated sludge (DEHS and DEHSold; 90-180 days) were collected upon construction of equipment for sludge dehydration in 2011. An analysis of total metal concentrations for Cu, Zn, Cr, Pb, Ni, Hg, Cd, Ba, As, Se, Sb, Co, Mo, Fe and Mn was performed by flame atomic absorption spectrometry (FAAS) and inductively coupled plasma-optical emission spectrometry (ICP-OES). The most recent results (year 2011) indicated a high concentration of heavy metals in PS samples, exceeding the MCLs (mg/kg dry matter): Cu (2122), Zn (5945), Hg (13.67) and Cd (6.29). In 2012 (until July), only a concentration of Cu exceeded MCL (928.75 and 1230.5 in DS and DEHS, respectively). A composition of sludge was variable through time, offering the limited possibility for future prediction. The sludge is being considered as a hazardous waste and a subject of discussion regarding disposal.

Major, minor and trace element content derived from aquacultural activity of marine sediments (Central Adriatic, Croatia)

Introduction and purposeStudies examining the environmental impact of marine aquaculture have increased significantly in number during the last few decades. The present paper investigates a region of rapid growth in intensive aquaculture and its influence on the local marine ecosystem.DiscussionThis study was undertaken with the specific aim of assessing the effect of fish farming on marine sediment at a farm near the island of Vrgada in the Central Adriatic. Data obtained regarding major (Si, Al, K, Na, Fe, Ca, Mg), minor (Mn, P, Ti) and trace (As, Au, Ba, Cd, Co, Cr, Cs, Cu, Ga, Hf, Hg, Mo, Nb, Ni, Pb, Rb, Sb, Sc, Se, Sr, Ta, Th, Tl, U, V, Y, Zn, Zr) elements were used to estimate the spatial and temporal distribution of metals in the sediment and their possible relationship with local aquacultural activity.ResultsAlthough the measured concentrations of heavy metals in sediment below fish cages were notably different and potentially a result of farming activity, the values were generally lower than background concentrations observed in the Central Adriatic. In contrast, concentrations of heavy metals at a reference site unaffected by aquaculture varied from lower levels to values even higher than those observed below the high-production cages. Furthermore, calculated environmental index values indicate that the sediment below the farm is either uncontaminated or suffers from only low levels of contamination.ConclusionSuch results suggest that the effect of observed fish farm activity on the local marine ecosystem is practically negligible.

Use of Stable Nitrogen Isotope Signatures of Anthropogenic Organic Matter in the Coastal Environment: The Case Study of the Kosirina Bay (Murter Island, Croatia)

In this study stable nitrogen isotope ratios of particulate matter POM, zooplankton and selected biota such as Mytilus galloprovincialis were used to assess the impact of anthropogenically derived organic matter from the untreated domestic sewage, municipal and industrial effluents on the coastal ecosystem of the Kosirina Bay (Murter Island). The differences in δ15N values observed in POM and organisms collected in Kosirina Bay as compared to POM and biota sampled at unaffected sites from the southern part of the Kornati Island and highly impacted Pirovac Bay revealed only a very minor effects of anthropogenic inputs of nutrients and organic matter which is most probably derived from a sewage outfall south of the Tužbina Island.

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.

Use of stable isotope composition variability of particulate organic matter to assess the anthropogenic organic matter in coastal environment (Istra Peninsula, Northern Adriatic)

Nitrogen and carbon stable isotope analysis of particulate organic matter (POM) was used to assess the impact of anthropogenically derived organic matter in coastal parts of the Istra Peninsula (Northern Adriatic). The investigation was conducted in areas potentially impacted and enriched with different amounts of organic matter. Elevated δ15N values in POM reflect enrichment of organic matter near the coast due to inadequate municipal infrastructure in cities and local septic systems as well as inputs from riverine terrestrial material. On the contrary, negative δ15N values reflect the depleting effect of purification plants. Significant differences in nitrogen stable isotope ratios were observed between western and southeastern coasts. The δ13C values show small depletion at sites with potentially greater anthropogenic impact. A weak temporal increase of δ15N from spring to late summer was observed. The results for nitrogen and carbon isotope ratios of POM and their comparisons with other areas suggest diverse amounts and sources of organic matter as well as differences in movement of floating POM within the water column. The δ15N and δ13C values reflect the ratios of marine and terrigenous organic matter, the latter being mainly anthropogenically influenced. The results finally suggest precaution in applicability of POM as tracers for detecting anthropogenic organic matter in marine coastal ecosystem.

Monazite in Hydrothermal Veins from Alinci, Yugoslavia

SummaryA new occurrence of monazite from Alinci, SE Yugoslavia, is described. Crystal morphology studies showed that crystals possess a platelike habit on T01 which we regard as a hitherto unknown morphological feature of monazite. The material has been analysed for uranium, thorium and rare earth element content using gamma spectrometry and inductively coupled argon-plasma atomic emission spectrometry (ICPAES). The monazite displays a complex chemical composition, essentially given as (REE+Y,Th,U,Fe)1.001P0.988O4. The infrared absorption spectra and X-ray diffraction data are in agreement with those for terrestrial monazite, although they indicate minor structural variations caused by the REE distribution in the Alinci monazite.ZusammenfassungEs wird ein neues Monazitvorkommen von Alinci, Jugoslawien, beschrieben. Kristallmorphologische Studien zeigten, daß die Kristalle einen plattigen Habitus nach (T01) aufweisen, eine nach Wissen der Autoren bisher unbekannte morphologische Erscheinung bei Monazit. Das Material wurde auf die Uran-, Thorium- und Seltenerdgehalte mit Gamma-Spektrometrie und induktiv gekoppelter Argonplasma-Atomabsorptions-Spektrometrie (ICPAES) analysiert. Der Monazit zeigt eine komplexe chemische Zusammensetzung, die im wesentlichen als (REE+Y,Th,U,Fe)1.001P0.988O4 angegeben werden kann. Die Ultrarotspektren und die Röntgenbeugungs-Daten stimmen mit jenen von terrestrischem Monazit überein, obwohl sie kleine strukturelle Variationen anzeigen, die durch die REE-Verteilung im Monazit von Alinci verursacht sind.

Trace metal levels in fossil human bone from the Bezdanjaca necropolis in Croatia

Elemental analysis of prehistoric human bone for the reconstruction of past environmental conditions, diets and migrations is a relatively new concept and can be a helpful tool in palaeoanthropology. The contents of Pb, Cu, Cd, Zn, Ca, Sr and Ba in fossil and recent human bone were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and differential pulse anodic stripping voltammetry (DPASV). Some variation among the measured elements was established, but strontium was found to be a suitable tracer for such bioanthropological investigations. The applied analytical techniques are suitable for such investigations because of the comparatively small amount of material required and great analytical precision.

Influence of soil characteristics on rare earth fingerprints in mosses and mushrooms: Example of a pristine temperate rainforest (Slavonia, Croatia)

The present study aims to investigate levels and distribution of rare earth elements (REE) in soils, mosses and mushrooms of a pristine temperate rainforest, a non-polluted natural system, in order to characterise their environmental availability and mobility. The multielement analysis of digested soil, moss and mushroom samples was performed by High Resolution Inductively Coupled Plasma Mass Spectrometry. The distribution of rare earths in mosses and mushrooms was found primarily affected by local pedological setting. Mosses displayed a consistent lithological signature with an almost insignificant REE fractionation compared to soils. Mushrooms showed differences in REE concentrations in certain parts of the fruiting body with regard to their main physiological function and indicated a significant impact of soil organic content on the overall REEs uptake. Results of our work highlight the importance of substrate characteristics on the initial levels of REEs in mosses and mushrooms. Moreover, this study provides baseline data on the rare earth element levels in mosses and mushrooms growing in a pristine forest area characterised by naturally elevated REE levels in the soil.