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The composition of isolated natural organic matter (NOM) fractions was studied by means of high pressure size-exclusion chromatography (HP-SEC), specific ultraviolet absorbance (SUVA) at 254 nm, total luminescence spectroscopy (TLS) and synchronous scanning fluorescence measurements. The HP-SEC, SUVA and TLS studies revealed that humic acids (HA) and hydrophobic acids (HOA) are composed of complex, aromatic and high molecular weight subunits. Hydrophobic neutrals (HON) consist of few groups of compounds with relatively low molecular sizes and a degree of condensed aromatic moieties. Similar characteristics were observed for hydrophilic acids (HIA) and bases (HIB). Obtained results also demonstrated that hydrophilic neutrals (HIN) are made of non-humic, aliphatic and low molecular weight components. Furthermore, the synchronous excitation-emission spectra indicated the presence of proteinlike constituents in HIB, HIN and HON fractions as well as lignin-derived constituents with relatively low molecular sizes in HIA.
The reported study describes the separation of humic substances (HS) dissolved in surface waters into hydrophilic and hydrophobic fractions with the SPE method onto StrataX (Phenomenex) columns. The separated fractions were analyzed with the HPLC-C18 (Merck column) method for relative polarity of humic (HA) and fulvic (FA) acids in the samples. Analyses were carried out on samples collected from 7 lakes constituting two cascade systems located in the same catchment of the Ełk River. During HPLC assays, an effect of size exclusion (SE) was observed, especially for the hydrophilic fraction. The HPLC analyses enabled us to demonstrate that in both hydrological systems the hydrophilic fraction contained mainly molecules with molecular weights exceeding 1,000Da and of practically equal relative polarity. Only in system II (five lakes) was the hydrophobic fraction strongly diversified quantitatively as well as in terms of molecular weight and polarity between the samples. Results of analysis show that this system was subject to a strong anthropogenic impact.
We have investigated trace metal accumulation in sediment and in insect larvae in a small lowland river, which is an ecosystem with a large load of organic allochthonous matter (leaf packs) due to its first stream order section running across forest as well as along the edge of a large city (anthropogenic enrichment). Two study sites of this reach are separated by recreation ponds. Mean annual discharge at the upstream site (BZA) was below 0.010 m3 s-1, while at downstream one (BZB) it increased to 0.037 m3 s-1, the latter flow highly fluctuating. Riverbed at BZA consisted of sand and cobbles, while at BZB of different fractions of sand (substrate inorganic index, SI, significantly lower). Beside benthic samples obtained at monthly intervals over a year, additional samples were collected three times over the year: in winter, late spring, and autumn from each site to get organisms (insect larvae) and sediment for metal analysis. Two species representing chironomids (Chironomus riparius and Prodiamesa olivacea) and one ephemeropterans (Ephemera danica) were selected for detailed analysis. Despite these three taxa being different in terms of morphology and/or physiology they belonged to the same functional feeding group, i.e. sediment feeders. We avoided species occurring in food chains in which sediment indirectly affected organisms. Correlations between metal concentrations in these aquatic organisms and their environments were recorded at the analysed sites. Higher index values of metal bioaccumulation (bioconcentration factor, BCF) by insects were obtained at the downstream site (BZB), with relatively low levels of toxicants. For example, 8.5 for Zn (in spring), 23.0 for Pb, 3.3 for Ni and 39.5 for Cd (last three values in autumn); each of them was characteristic for P. olivacea. In turn, for the ephemeropteran species E. danica the respective highest BCF values were: 4.8 for Cu (in spring) and 1.6 for Mn (in autumn). On the other hand, lower BCF indices we gained at the BZA site, where higher concentrations of metals in sediment were recorded; for example, 2.7 for Zn (in autumn, P. olivacea), 4.3 for Pb, 6.8 for Cd, 4.3 for Cu (each value in spring, C. riparius). An exception of this relation was 5.6 for Ni (C. riparius, in autumn), and 1.8 for Mn (C. riparius, in spring) where BCF reached higher values at BZA than at BZB. Note that C. riparius did not appear at BZA during the studied period. Despite this species’ absence the above mentioned relation may testify to the ability of sediment feeders to regulate metal contaminant content in their tissues. It seems that natural organic load rather than low levels of metal toxicants decided about macroinvertebrate assemblages in the study river.
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