How do certain atmospheric aerosols affect Cu-binding organic ligands in the oligotrophic coastal sea surface microlayer?

It is still unclear how the chemical speciation of Cu in surface seawater is impacted by aerosols from various sources deposited on the sea surface, which is surprising, considering the environmental importance of Cu. Therefore, we used voltammetry to investigate Cu complexing capacity (CuCC) in the sea surface microlayer (SML) and in the underlying water (ULW) of the oligotrophic middle Adriatic Sea during February-July 2019. The focus was on the impacts of specific atmospheric processes such as open-fire biomass burning (BB), pollination season and Saharan dust intrusion. The presence of ligand class L2 (19.9-392.0, average 63.8, median 43.1) nM; log K2 (8.3-10.2, average 9.6, median 9.6) was observed in all samples, while ligand class L1 (40.5-76.1, average 53.6, median 48.9) nM; log K1 (10.3-11.1, average 10.6, median 10.5) was found in only 25% of SML samples. Throughout the period, the SML was enriched with organic ligands by a factor of up to 9.1 compared to the ULW, mainly due to the high sensitivity of the SML to specific atmospheric depositions. In addition, measurements with corresponding specific model aerosols were conducted to analyse their impacts on CuCC. Pollen directly affected CuCC in the SML by increasing the concentration of allochthonous ligands such as proteins. The deposition of BB aerosols rich in nutrients and trace metals stimulated the biological production of organic ligands, showing an indirect effect on CuCC delayed by up to two weeks. Finally, Saharan dust had a negligible impact on CuCC. This study illustrates the susceptibility of oligotrophic coastal area to the effects of pollen and open-fire BB aerosols in altering the Cu-binding organic ligands in the SML.

Assessing trace metal contamination and organic matter in the brackish lakes as the major source of potable water.

On small and medium karstic coastal islands in the Adriatic Sea, brackish lakes are often the only source of freshwater. Therefore, it is important to adequately evaluate the biogeochemical processes occurring in these complex water systems, as well as to determine the origin of contaminants present. In this study, the distribution and origin of trace metals (Tl, Hg, Cd, Pb, Cu, Zn, Ni, Co) and organic matter in the water column, sediment, and surrounding soil of the brackish lakes on Mljet Island, South Adriatic Sea, Croatia, were evaluated. Thallium and mercury concentrations in the lake water were up to two orders of magnitude higher compared to ranges found in the adjacent coastal sea water. Elevated thallium concentrations were of anthropogenic origin resulting from previous use of rodenticide, while elevated mercury content was naturally enhanced. Levels for the other metals were characteristic of uncontaminated water systems. Speciation modelling showed that dissolved trace metals such as Cu, Pb, and Zn were mostly associated with organic matter, while Tl, Co, and Ni were present predominantly as free ions and inorganic complexes. The presence of organic matter (OM) clearly influenced the speciation and distribution of some trace metals. OM was characterised by the determination of the complexing capacity for Cu ions (CuCC), surface active substances, and catalytically active compounds. Reduced sulphur species (glutathione and other thiols) representing significant Cu-binding ligands were determined and discussed as well.

Adsorption/desorption of biomacromolecules involved in catalytic hydrogen evolution.

Previously, it has been shown that proteins and some polysaccharides (PSs) catalyse hydrogen evolution, producing electrochemical signals on mercury electrodes. The catalytic hydrogen evolution reaction (CHER) of the above-mentioned biomacromolecules was studied by voltammetric and chronopotentiometric stripping (CPS) methods. To obtain more information about electrode processes involving CHER, here we used protein such as BSA, and chitosan as a PS; in addition, we investigated dextran as a control PS not involved in CHER. We studied biomacromolecules by phase-sensitive alternating current (AC) voltammetry. Using phase-in AC voltammetry, for CHER-involved biomacromolecules we observed a CHER peak at highly negative potentials, similar to that observed with other voltammetric and CPS methods. On the other hand, by means of the adsorption/desorption processes studied in phase-out AC voltammetry, we uncovered a sharp and narrow decrease of capacitive current in the potential range of the CHER peak, denominated as the tensammetric minimum. This minimum was closely related to the CHER peak, as demonstrated by similar dependences on specific conditions affecting the CHER peak such as buffer capacity and pH. A tensammetric minimum was not observed for dextran. Our results suggest specific organization of biopolymer layers at negative potentials observed only in biomacromolecules involved in CHER.

Immunoassays of chemically modified polysaccharides, glycans in glycoproteins and ribose in nucleic acids.

Glycosylation of proteins plays an important role in health and diseases. At present new simple and inexpensive methods of glycoprotein analysis are sought. We developed a monoclonal antibody Manost 2.1 in mice after immunization with the adduct of mannan with Os(VI)temed complex (temed is N,N,N',N'-tetramethylethylenediamine). The specificity of this antibody to different biomolecules treated with Os(VI)temed was tested using dot blot immunoassay. Manost 2.1 showed specificity toward Os(VI)temed-modified polysaccharides, glycoproteins and ribonucleotide at the 3'-end in DNA. The antibody recognized neither the unmodified compounds nor the non-glycosylated proteins treated with Os(VI)temed. We also performed western blotting and Coomassie silver blue staining of mixtures of biomacromolecules treated with Os(VI)temed and identified specifically the modified glycoproteins. The immunochemical method using Manost 2.1 was compared with electrochemical analyses based on redox signals of the Os(VI)temed adducts, with similar results in terms of sensitivity. This new antibody-based approach opens the door for rapid and inexpensive analysis of glycans and glycoproteins in various scientific and medical fields, including cancer research and the future application of glycoprotein detection in clinical practice.

Carbohydrate polymers as constituents of exopolymer substances in seawater, their complexing properties towards copper ions, surface and catalytic activity determined by electrochemical methods.

The goal of this study was to investigate to which extent polysaccharides (PS) contribute to the complexing capacity for copper ion (LT), to determine their property of surface activity and evaluate their capability to cause the catalytic hydrogen evolution wave (peak "H") due to their adsorption and the catalytic groups in their structure. Complexing capacities and apparent stability constants (Kapp) were measured electrochemically for model polysaccharides (PS): carrageenans (κ-, ι- and λ-), chondroitin sulfate, dextran, dextran sulfate, Na-alginate and humic material. Cu-complexing capacities were determined for Na-alginate (logKapp=8.32) and chondroitin sulphate (logKapp=8.14). PS adsorb on different surfaces due to their amphyphylic properties and on that way they could increase the interaction of copper ions with these surfaces by forming the surface complexes with Cu ions.

Copper complexing properties and physico-chemical characterisation of the organic matter in Greek herbal infusions.

Complex formation is among the mechanisms affecting metals' bioaccessibility. Evaluating the extent of interactions between trace elements and several constituents of food items is of great interest. This paper examines the release of copper-complexing ligands in herbal infusions of 13 aromatic plants commonly used in Greece. The concentration of ligands (LT) and the copper-binding strength (logKapp) of herbal infusions were determined with Differential Pulse Anodic Stripping Voltammetry (DPASV). All herbal infusions were found to release Cu complexing ligands, at concentrations ranging from 8.8 to 112.5 µM in rosemary and marjoram, respectively. In all infusions the total copper concentrations were lower than the corresponding LT values, indicating that Cu is fully complexed. Aiming to partially characterise the physico-chemical properties of the released organic material, the surface active substances (SAS), reduced sulphur species (RS) and catalytically active compounds (CAC) were measured, for the first time, in herbal infusions by sensitive electrochemical techniques.

Copper complexing properties of exudates and metabolites of macroalgae from the Aegean Sea.

Macroalgae are a significant source of extracellular organic material in the coastal areas of the Mediterranean, including organic ligands which serve as modulators of metal complexing capacity. This paper examines the release of copper-complexing ligands by 24 macroalgal species, including chlorophyta, rhodophyta, ochrophyta as well as Posidonia oceanica, common throughout the Mediterranean. Metabolites isolated from the algae Dictyota dichotoma and Pterocladiella capillacea were examined for the first time regarding their Cu-complexing properties. The concentration of ligands (LT) and the copper-binding strength (logKapp) of exudates and metabolites were determined by electrochemical methods. All algal species released ligands giving LT concentrations ranging from 109 to 744 nM in unfiltered samples. An increase in the concentration of ligands up to 15 times in comparison to the blank was observed after 48 h of culturing macroalgae in artificial seawater. The binding strength (log Kapp) varied among species from 7.0 to 8.6, except for the metabolites for which it was lower (log Kapp=6). Most of the ligands released were in the dissolved phase, with the contribution of particulate and/or colloidal organic matter (up to 46% of total ligands) appearing to be important only in specific macroalgal species.