Metal bioaccumulation in stygophilous amphipod Synurella ambulans in the hyporheic zone: The influence of environmental factors.

Given the increasing need to protect vulnerable freshwater ecosystems and make them more resilient to human use and climate change, biomonitoring of the hyporheic zone (HZ), which plays a critical role in pollution attenuation, is essential. The aim of the present study was to assess the potential of the amphipod species Synurella ambulans as a bioindicator of metal contamination in the HZ of the Sava River (Croatia). Amphipods were collected during the four seasons at two sampling sites (average sampling depth 55 cm) differing in type (agricultural and urban) and intensity (diffuse and point source contamination) of anthropogenic influence, one located upstream (Medsave), and the other downstream (Jarun) of the wastewater treatment plant discharge. Concentrations of Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Rb, Sn, Zn, Ca, K, Mg and Na were measured in the interstitial water, sediments and specimens of S. ambulans by HR ICP-MS. Physicochemical parameters (temperature, DO, O2 saturation, pH, conductivity, alkalinity, total water hardness, CODKMnO4, nutrients) were measured in the interstitial water, while organic carbon was measured in the interstitial water and sediments. Metal concentrations in interstitial water and sediments were below thresholds set by environmental quality standards. Metal concentrations in S. ambulans were classified as follows: higher at the Jarun site (Al, Cr, Fe, Ni, Pb, Sn), higher at the Medsave site (Cd, Cu, Rb) and mostly comparable at both sites (Co, Mn, Zn). Bioaccumulation factors were generally higher at Jarun, with average values ranging from 322 to 143,278 L kg-1. Bioaccumulation of metals in S. ambulans depended on various environmental factors, with metal exposure level and dissolved macro elements showing the strongest association with metals accumulated in S. ambulans. The findings provided the first evidence on the suitability of S. ambulans as a good bioindicator of chronic metal contamination in the HZ.

Simultaneous analysis of butyltins and total tin in sediments as a tool for the assessment of tributyltin behaviour, long-term persistence and historical contamination in the coastal environment.

This study presents a new approach for the investigation of tributyltin (TBT) behaviour and fate in the marine environment. The approach is based on a simultaneous analysis of butyltins (BuTs) and total Sn in sediments, thus enabling an assessment of long-term persistence and historical input of TBT. The study also presents first evaluation of the extent to which the TBT-antifouling paints contribute to the contamination of coastal environments with inorganic Sn; it was demonstrated that the inorganic Sn in the investigated areas primarily originates from TBT degradation. The study was conducted by analyzing BuTs and total Sn in sediments from 34 locations along the Croatian Adriatic coast. The results revealed that 85% of the locations were contaminated with both BuTs and inorganic Sn. The share of Æ©BuTs/total Sn was low (<10%) even in sediments with low TBT degradation efficiency (TBT/Æ©BuTs >40%), demonstrating that only small portion of TBT introduced into the water column reached the sediment before being degraded. This means that recent TBT input into the marine environment may be at least 10 times higher than the amount estimated if only BuTs levels in sediments are considered. It was also demonstrated that TBT concentration in sediments with TOC <1% is not a good indicator of the overall pollution level, even if TBT/TOC approach is used in pollution assessment. Finally, in situ investigation showed that resuspension of contaminated sediments leads to significant release of MBT and DBT into the water column, whereas TBT mainly remains in sediment.

Dissolved organic carbon and surface active substances in the northern Adriatic Sea: Long-term trends, variability and drivers.

The paper presents a unique time series of organic matter content (dissolved organic carbon, DOC, and its surface active substances fraction, SAS) collected in the northern Adriatic along the Po-Rovinj transect between 1998 and 2017. The data were collected on a monthly or bimonthly basis. Seasonal variance of organic matter content does not exceed 30% of its total variance, while the DOC and the SAS trends are significantly negative and positive, respectively, over the whole transect. The organic matter content, however, exhibits pronounced interannual and decadal changes, with periods of high and low carbon content and evident changes in composition of the SAS content. The changes indicate altering episodes between eutrophication and oligotrophication, embedded in the overall oligotrophication trend in the considered period. Both series were correlated with the potential local and regional yearly-averaged drivers in both atmosphere and sea. DOC is most strongly (significant at 99%) correlated with the Po River discharges, at the phase lag of -1 to -2 years. For the SAS, the largest correlations (significant at 99%) are obtained with the Adriatic-Ionian Bimodal Oscillating System index (BiOS index), at the phase lag of -3 to -4 years. Correlations between the organic matter content and the hemispheric or the regional climate indices (North Atlantic Oscillation, East Atlantic/West Russia, East Atlantic, Scandinavian, and Mediterranean Oscillation) are much lower and only sparsely significant at 95% at some phase lags. The same was found for the other local drivers (precipitation and net heat flux). Our analysis highlights the importance of remote processes, like the BiOS, that weren't previously considered to shape the biogeochemical properties of such shallow coastal region impacted by freshwater load. To properly assess such impacts, long-term ecological monitoring and homogenized data series are required.

The assessment of metal contamination in water and sediments of the lowland Ilova River (Croatia) impacted by anthropogenic activities.

The aim of the present study was to assess physico-chemical water parameters, granulometric sediment characteristics and concentrations of trace and macroelements in the water and sediments of the Ilova River. Samplings were conducted at three sampling sites (near villages Maslenjaca, Ilova and Trebez) along the Ilova River, differing in the source and intensity of the anthropogenic influence. This study indicated disturbed environmental conditions, most pronounced in the downstream part of the river (Trebez village) impacted by the activity of fertilizer factory. Water from the Ilova and Maslenjaca villages was of good quality, whereas COD, nitrates and phosphates exceeded the good quality levels in Trebez village. Trace and macroelement concentrations in water were mostly below thresholds set by environmental quality standards at all locations, but levels of Al, As, Cd and Ni were few times higher in Trebez village than at other locations. Metal contamination assessment of sediments (trace and macroelement concentrations, contamination and enrichment factor, pollution load index) confirmed deteriorated environmental quality in Trebez village. However, the overall assessment performed in this study revealed that anthropogenic impact was still not particularly strong in the Ilova River ecosystem. Nevertheless, the observed water and sediment characteristics serve as a warning and suggest that stricter protection measures should be initiated, including continuous monitoring and comprehensive quality assessment of the downstream part of the Ilova River, especially because it is a part of the protected area of the Lonjsko Polje Nature Park.

Dissolved organic carbon as potential indicator of global change: A long-term investigation in the northern Adriatic.

Dissolved organic carbon (DOC) is an essential component of the biogeochemical marine system, effecting biological and chemical reactions that take place in the sea. DOC represents a dynamic component of the global carbon cycle. This paper reports 25years of measurements of DOC content and distribution at seven stations along the transect Po River delta - Rovinj in the northern Adriatic (NA). The results show strong temporal and spatial variability: (1) The highest average DOC concentrations were observed in 1998 and 2002 (143µmol/L and 137µmol/L, respectively); (2) The minimum average DOC was recorded in 2006 (88µmol/L) and (3) The short-term DOC accumulation (up to 203, average 102µmol/L) for the years 2009 to 2012, was observed during the summer and autumn months followed by unusually low DOC concentrations during the winter and spring. The DOC results from the more recent monitoring at the same stations indicate primarily oligotrophic characteristics of the NA seawater (88µmol/L). The results of DOC variability and distribution in the NA appears to be strongly influenced by complex circulation patterns. This paper provides a "link" between the Ionian circulation and the NA ecosystem as a part of the recently identified Adriatic-Ionian Bimodal Oscillating System (BiOS). A good agreement between the BiOS oscillation and other variables related to the DOC concentration, like the NA A and B winter types, the Po River discharge, salinity, chlorophyll a, occurrence of hypoxic-anoxic conditions, eutrophication and oligotrophication, suggests that DOC might be a good tool and indicator of global change.