Organic complexation of copper in throughfall and open eld bulk deposition: Inuence of the tree canopy of Mediterranean forest ecosystems Sotirios Karavoltsos a, * , Fotios Fotiadis a , Panagiotis Michopoulos b , Aikaterini Sakellari a , Marta Plav si c c , Athanassios Bourletsikas b , Kostas Kaoukis b , Nikolaos S. Thomaidis d , Manos Dassenakis a , Michael Scoullos a a National and Kapodistrian University of Athens, Department of Chemistry, Laboratory of Environmental Chemistry, Panepistimiopolis,157 84, Athens, Greece b H.A.O. DEMETER, Institute of Mediterranean Forest Ecosystems, Terma Alkmanos, 115 28 Athens, Greece c RuCer Boskovic Institute, Center for Marine and Environmental Research, P.O. Box 180,10002 Zagreb, Croatia d National and Kapodistrian University of Athens, Department of Chemistry, Laboratory of Analytical Chemistry, Panepistimiopolis,157 84, Athens, Greece highlights graphical abstract Cu complexation in forest throughfall was studied for the rst time by DPASV. Samples were collected from two different Mediterranean forest ecosystems. In throughfall (TF) and bulk deposi- tion (BD) copper was fully complexed. Cu ligands concentrations were determined 3e4 fold higher in TF than in BD. HULIS seem to be the most wide- spread type of ligands in both type of precipitations. article info Article history: Received 21 April 2016 Received in revised form 16 September 2016 Accepted 26 September 2016 Available online 2 October 2016 Handling Editor: Martine Leermakers Keywords: Throughfall Bulk deposition Copper complexing capacity Apparent stability constant Canopy abstract The complexing capacity for Cu ions (L T ) and the apparent stability constant values (logK app ) were measured in throughfall (TF) and open eld bulk deposition (BD), at two Mediterranean forest ecosys- tems of western Greece. L T was measured for the rst time in the TF of natural forests. Concentrations of L T were three-to-four-fold higher in TF (mean ± st.dev: 2014 ± 769 nM for Varetada and 1565 ± 595 nM for Karpenissi) compared to those in BD (531 ± 517 nM and 468 ± 321 nM, respectively). In all TF and BD samples, L T concentrations were signicantly higher than the corre- sponding total Cu concentrations, indicating that Cu was fully complexed. The L T /TOC ratios in TF were found comparable between the two study sites (235 ± 149 nM mg 1 C for Varetada and 256 ± 233 nM mg 1 C for Karpenissi) and with those of BD (226 ± 257 and 163 ± 163 nM mg 1 C, respectively). The determined mean logK app values were almost identical in TF (6.8 ± 0.7 at Varetada; 6.8 ± 0.6 at Karpenissi) and BD (6.5 ± 0.6 at Varetada; 6.8 ± 0.3 at Karpenissi), pointing to the fact that regardless of the enrichment of TF in ligands (L T(TF) > L T(BD) ) the type of binding sites remain the same. * Corresponding author. E-mail address: skarav@chem.uoa.gr (S. Karavoltsos). Contents lists available at ScienceDirect Chemosphere journal homepage: www.elsevier.com/locate/chemosphere http://dx.doi.org/10.1016/j.chemosphere.2016.09.131 0045-6535/© 2016 Elsevier Ltd. All rights reserved. Chemosphere 167 (2017) 28e35