ࡱ > V X S T U d 5@ K bjbj22 X X M % 4 h
å " . 0 0 0 0 0 0 $ R v T ) T } ) ) )
6 ) . ) ) ) v |H k' F " 0 å T B w ' ` w w D ) T T Y) C o n s t a n t c u r r e n t c h r o n o p o t e n t i o m e t r i c s t r i p p i n g a n a l y s i s o f N - c a t a l y s t i n s o d i u m c h l o r i d e s o l u t i o n a n d s e a w a t e r
S l a a n a S t r m e
k i * , M a r t a P l a v ai , B o ~e n a o s o v i
R u e r B o ak o v i I n s t i t u t e , D i v i s i o n f o r M a r i n e a n d E n v i r o n m e n t a l R e s e a r c h ,
B i j e n i
k a 5 4 , P . O.Box 180, 10 002 Zagreb, Croatia
* Corresponding author, e-mail: HYPERLINK "mailto:strmecki@irb.hr" strmecki@irb.hr
Other authors: HYPERLINK "mailto:plavsic@irb.hr" plavsic@irb.hr , HYPERLINK "mailto:cosovic@irb.hr" cosovic@irb.hr
Abstract
Catalytic properties and surface activity of nitrogen containing polymeric organic material (N-POM) were analyzed by constant current chronopotentiometric stripping analysis (CPSA) and alternating current (AC) voltammetry in sodium chloride solution (pH 8) and seawater. CPSA proved to be a suitable method for determination of low concentrations of N-POM in seawater by measuring its presodium catalytic peak H. A protein human serum albumin (HSA) (15 % of N) was used as a model compound and the concentration of N-POM from natural seawater samples was expressed in HSA concentration equivalents. Peak H represents an additional parameter for characterization of natural organic matter.
Keywords: N-containing polymeric organic material, peak H, chronopotentiometric stripping analysis, seawater samples
Introduction
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Acad Sci Czech Republ, Inst Biophys, Kralovopolska 135, CZ-61265 Brno, Czech Republic
Acad Sci Czech Republ, Inst Biophys, CZ-61265 Brno, Czech Republic
Masaryk Univ, Fac Sci, Dept Theoret & Phys Chem, CZ-61137 Brno, Czech RepublicDetermination of metallothionein at the femtomole level by constant current stripping chronopotentiometryAnalytical ChemistryAnalytical Chemistry48017320differential-pulse polarographycarbon electrodesrat-liverelectrochemical-behaviormercury-electrodesanimal-tissuesmetal-ionsvoltammetryproteinscadmium20014801-48070003-2700ISI:000171696800007<Go to ISI>://000171696800007English[3]. Therefore, it is successfully applied for the determination of low metal ion concentrations ADDIN EN.CITE Riso1997252517Riso, R. D.LeCorre, P.Chaumery, C. J.Riso, RD
Roscoff Univ Bretagne Occidentale,Upr Cnrs 9042,Lab Oceanog Chim,6 Rue Le Gorgeu,Bp 809,F-29285 Brest,France
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Queens Univ Belfast, Sch Chem, David Keir Bldg, Belfast BT9 5AG, Antrim, North Ireland
Queens Univ Belfast, Sch Chem, Belfast BT9 5AG, Antrim, North Ireland
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Univ Porto, Fac Engn, Dept Engn Quim, CTQAA, P-4099 Oporto, Portugal
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Queens Univ Belfast, Sch Chem, Belfast BT9 5AG, Antrim, North Ireland
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Acad Sci Czech Republ,Inst Biophys,Brno 61265,Czech Republic
Univ Nacl Cordoba,Dept Quim Fis,Ra-5000 Cordoba,Argentina
Pontificia Univ Catolica Rio De Janeiro,Dept Chem,Rio Janeiro,Brazil
Ritsumeikan Univ,Dept Chem,Kusatsu,JapanPotentiometric stripping analysis of bioactive peptides at carbon electrodes down to subnanomolar concentrationsAnalytica Chimica ActaAnalytica Chimica ActaAnal. Chim. Acta493321potentiometryadsorptive stripping voltammetrybioactive peptideschronopotentiometrypeptide-modified carbon paste electrodescyclic voltammetrynucleic-acidsproteinsquantitiesDNA199649-570003-2670ISI:A1996VN99000006<Go to ISI>://A1996VN99000006English[9], proteins ADDIN EN.CITE Kizek2001181817Kizek, R.Trnkova, L.Palecek, E.Palecek, E
Acad Sci Czech Republ, Inst Biophys, Kralovopolska 135, CZ-61265 Brno, Czech Republic
Acad Sci Czech Republ, Inst Biophys, CZ-61265 Brno, Czech Republic
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Pontificia Univ Catolica Rio De Janeiro,Dept Chem,Rio Janeiro,Brazil
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Acad Sci Czech Republ, Inst Biophys, CZ-61265 Brno, Czech Republic
Acad Sci Czech Republ, Inst Biophys, CZ-61265 Brno, Czech Republic
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Rudjer Boskovic Inst, Ctr Marine & Environm Res, POB 180, HR-10002 Zagreb, Croatia
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Univ Washington, Sch Oceanog, Box 357940, Seattle, WA 98195 USA
Univ Washington, Sch Oceanog, Seattle, WA 98195 USA
Univ Bristol, Biogeochem Ctr, Bristol BS8 1RJ, Avon, England
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Ctr Marine & Environm Res, Rudjer Boskovic Inst, Zagreb 10000, Croatia
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Rudjer Boskovic Inst, Ctr Marine Environm Res, Bijenicka 54, Zagreb 10000, Croatia
Rudjer Boskovic Inst, Ctr Marine Environm Res, Zagreb 10000, Croatia
Ca Foscari Univ, Dept Environm Sci, I-30121 Venice, ItalyMucopolysaccharide transformation by sulfide in diatom cultures and natural mucilageMarine Ecology-Progress SeriesMarine Ecology-Progress Series17263mucilagebenthic diatomscon-a lectinmicroscopyadriatic seaanoxiareduced sulfur speciesvoltammetrytransparent exopolymer particlessurface-active substancestyrrhenian searogoznica lakeadriatic seaseawaterpolysaccharidesphytoplanktonmercuryadsorption200317-270171-8630ISI:000187934600002<Go to ISI>://000187934600002English[23] already reported about CPS detection of peak H catalyzed by sulphur atoms in polysaccharides excreted from plankton cultures exposed to anoxic conditions. Their catalytic peak H appears at Ep = -1.50 V. A similar peak is obtained in a model solution of sulphated polysaccharide, - c a r r a g e e n a n , e x t r a c t e d f r o m r e d m a r i n e a l g a e A D D I N E N . C I T E < E n d N o t e > < C i t e > < A u t h o r > P l a v s i c < / A u t h o r > < Y e a r > 1 9 9 8 < / Y e a r > < R e c N u m > 1 3 < / R e c N u m > < r e c o r d > < r e c - n u m b e r > 1 3 < / r e c - n u m b e r > < r e f - t y p e n a m e = " J o u r n a l A r t i c l e " > 1 7 < / r e f - t y p e > < c o n t r i b u t o r s > < a u t h o r s > < a u t h o r > P l a v s ic, M.Cosovic, B.Plavsic, M
Rudjer Boskovic Inst, Ctr Marine & Environm Res, POB 1016, HR-10001 Zagreb, Croatia
Rudjer Boskovic Inst, Ctr Marine & Environm Res, HR-10001 Zagreb, CroatiaAdsorption of carrageenans on mercury surface in sodium chloride solution and seawaterCroatica Chemica ActaCroatica Chemica Acta233712electrodesystemsalgaeions1998233-2430011-1643ISI:000074204000004<Go to ISI>://000074204000004English[24]. A more negative peak H, at around -1.7 V, was observed in seawater samples and a connection with the presence of organic matter containing N catalytic atoms was supposed. Peak potential is a well known characteristic for a qualitative analysis ADDIN EN.CITE Bard198048486Electrochemical methods: Fundamentals and ApplicationsBard198048486Electrochemical methods: Fundamentals and Applications[25], in our case S- and N-containing OM. Therefore, in the present work catalytic activity of protein HSA which has in the structure 15 % of nitrogen atoms and of OM containing N-atoms in natural seawater was investigated in details. As the most important segment in catalysis is a contact of catalyst itself and the electrode surface ADDIN EN.CITE Mairanovskii196845456Catalytic and Kinetic Waves in Polarography[14], surface activity was examined, too. Alternating current (AC) voltammetry (out of phase mode) is widely applied for analysis of adsorption of surface active substances (SAS) on different phase boundaries by measuring the double layer capacitive current ADDIN EN.CITE Cosovic1998282817Cosovic, B.Vojvodic, V.Cosovic, B
Rudjer Boskovic Inst, Ctr Marine & Environm Res, POB 1016, CHR-10001 Zagreb, Croatia
Rudjer Boskovic Inst, Ctr Marine & Environm Res, CHR-10001 Zagreb, CroatiaVoltammetric analysis of surface active substances in natural seawaterElectroanalysisElectroanalysisElectroanalysisElectroanalysis429106surfactantsstripping voltammetrytriton x-100capacitanceac voltammetryorganic-matterhydrophobic fractionsea-watermicrolayeradsorptioncolloidsbehaviorsamplesestuary1998429-4341040-0397ISI:000074468400014<Go to ISI>://000074468400014EnglishCosovic1998282817Cosovic, B.Vojvodic, V.Cosovic, B
Rudjer Boskovic Inst, Ctr Marine & Environm Res, POB 1016, CHR-10001 Zagreb, Croatia
Rudjer Boskovic Inst, Ctr Marine & Environm Res, CHR-10001 Zagreb, CroatiaVoltammetric analysis of surface active substances in natural seawaterElectroanalysisElectroanalysisElectroanalysisElectroanalysis429106surfactantsstripping voltammetrytriton x-100capacitanceac voltammetryorganic-matterhydrophobic fractionsea-watermicrolayeradsorptioncolloidsbehaviorsamplesestuary1998429-4341040-0397ISI:000074468400014<Go to ISI>://000074468400014EnglishPlavsic2000363617Plavsic, M.Cosovic, B.Cosovic, B
Rudjer Boskovic Inst, Ctr Marine & Environm Res, POB 180, HR-10002 Zagreb, Croatia
Rudjer Boskovic Inst, Ctr Marine & Environm Res, HR-10002 Zagreb, CroatiaAdsorption properties of different polysaccharides on mercury in sodium chloride solutionsElectroanalysisElectroanalysisElectroanalysisElectroanalysis8951212voltametry (ac, cyclic)capacitanceadsorptionpolysaccharidesmucilagesurface-active substancesbiological-activitiesseawatersugarsoceanacidsdeepsea2000895-9001040-0397ISI:000088963200004<Go to ISI>://000088963200004EnglishCosovic2007484817Cosovic, B.Leko, P. O.Kozarac, Z.Cosovic, B
Ctr Marine & Environm Res, Ruoer Boskovic Inst, POB 180, Zagreb 10002, Croatia
Ctr Marine & Environm Res, Ruoer Boskovic Inst, Zagreb 10002, Croatia
Univ Zagreb, Min & Geol Petrol Engn Dept, Zagreb 10000, CroatiaRainwater dissolved organic carbon: Active substances by electrochemical characterization of surface methodElectroanalysisElectroanalysisElectroanalysisElectroanalysis20771919-20ac voltammetryadsorptionorganic matterrainwatersurface active substanceschloride solution interfacemercury-electrodefatty-acidswatertensionadsorptionaerosolsdropletsseawatermodel20072077-20841040-0397ISI:000250129100011<Go to ISI>://000250129100011English[26-28]. Therefore, this method was suitable to be used in our experiment. HSA solution was also measured with square wave (SWV) and cyclic voltammetry (CV). Because of the modified pulse excitation signal which has symmetric square shaped form, SWV is the most sensitive and the fastest among the voltammetric methods ADDIN EN.CITE Bard198048486Electrochemical methods: Fundamentals and ApplicationsKounaves199747476Handbook of Instrumental Techniques for Analytical ChemistryUpper Saddle River[25,29]. The concentration of (N-POM) in seawater samples was determined by CPSA and quantitatively expressed as equivalents of a model protein HSA for which a calibration line has been done in a concentration range of the expected N-POM concentrations in natural seawater. Seasonal change of N-POM was also observed and compared to SAS and DOC changes.
Experimental
Instrumentation
All electrochemical work was done using 663 VA Stand multimode electrode system (Metrohm, Herisau, Switzerland) a n d A u t o l a b A n a l y z e r t y p e I I I ( E c o C h e m i e , U t r e c h t , T h e N e t h e r l a n d s ) . S t a t i c m e r c u r y d r o p e l e c t r o d e ( S M D E ) w a s u s e d a s a w o r k i n g e l e c t r o d e , A g / A g C l ( 3 M K C l ) w a s a r e f e r e n c e e l e c t r o d e a n d g l a s s y c a r b o n ( G C ) r o d w a s a n a u x i l i a r y e l e c t r o d e . S o l u t i o n w a s s t i r red with a Teflon stirrer adjusted to 3000 turns per minute.
Dissolved organic carbon (DOC) content in seawater samples has been measured after a procedure of high temperature catalytic oxidation (HTCO) with TOC-VCPH instrument (Shimadzu, Japan).
Methods
Model protein solution and OM from natural seawater samples were electrochemically analyzed using potentiometric and voltammetric methods. Emphasis was on chronopotentiometric stripping analysis (CPSA) with constant current stripping mode, a phase-sensitive a l t e r n a t i n g c u r r e n t ( A C ) v o l t a m m e t r y o u t o f p h a s e m o d e ( p h a s e a n g l e , = 9 0 o ) , c y c l i c ( C V ) a n d s q u a r e - w a v e ( S W V ) v o l t a m m e t r y .
C o m m o n m e a s u r e m e n t c o n d i t i o n s f o r a l l e l e c t r o c h e m i c a l m e t h o d s w e r e : a c c u m u l a t i o n p o t e n t i a l E A = - 0 . 6 V a n d t i m e o f a c c u m u l a t i o n t A = 6 0 s , w i t h s t i r r i n g . P a r a m e t e r s b e i n g c h a r a c t e r i s t i c f o r C P S A w e r e : c o n s t a n t r e d u c t i o n c u r r e n t I = - 1 A a n d m a x i m u m t i m e o f m e a s u r e m e n t 5 s , w h e r e a s i n A C v o l t a m m e t r y t h o s e w e r e : f r e q u e n c y f = 7 7 s - 1 , s t e p p o t e n t i a l E s = 0 . 0 1 V a n d a m p l i t u d e a = 0 . 01 V, in SWV step potential Es = 0.01 V, amplitude a = 0.05 V and frequency f = 100 s-1, in CV step potential Es = 0.01 V and scan rate v = 1 V s-1. The whole procedure was maintained with GPES software, version 4.9.
The peak characteristics in CPSA (peak potential Ep, height (dE / dt)-1 and area - stripping time), in SWV and CV (peak potential Ep, current I and charge q) were defined after applying linear baseline. In AC voltammetric measurements the decrease of the capacitive current in the presence of SAS was measured at the potential of E = -0.6 V.
CPS and AC measurements were performed in the presence of dissolved oxygen. In contrast, the response in SWV and CV is very sensitive to the presence of oxygen, so it was important to eliminate it from solution by purging it with nitrogen for 5 minutes before each measurement. Nitrogen pressure was then maintained over the solution.
Reagents and electrolytes
A protein human serum albumin (HSA) (Sigma, Aldrich) with 15.7 % of nitrogen content, essentially fatty acid free, with molar mass of 69 kDa was a model polymer substance. One electrolyte solution was 0.55 M NaCl, corresponding to the composition of seawater but without seawaters micro- and macroconstituents. It was prepared by diluting saturated 5.5 M NaCl solution which was made by dissolution of supra pure solid NaCl (Sigma, Aldrich). pH of 0.55 M NaCl was maintained at 8 by adding 2x10-3 M NaHCO3 to the solution. Stock solution of NaHCO3 (2x10-2M) was prepared daily from solid NaHCO3 (Sigma, Aldrich). The other electrolyte was OM free seawater which was prepared after filtration of seawater trough GF/F filter (Whatman) with pore size 0.7m, UV irradiation for 24 hours and by keeping it in a mixture with charcoal for 24 hours. After that the charcoal was filtered off and OM free seawater was obtained. No buffer was added to the seawater electrolyte as seawater is naturally a buffer solution containing carbonate buffer system ADDIN EN.CITE Stumm1981226<style face="normal" font="default" charset="238" size="100%">Aquatic Chemistry</style>[30]. All stock solutions were prepared in MQ water from Milli-Q filter apparatus (Millipore, USA).
Seawater samples ware collected in the Northern Adriatic station 101 (Fig. 1) in 4 seasons: June and October 2008 and in January and March 2009, at surface (0.5 m depth) and bottom (~31 m depth). 25 cm3 of sample was analyzed in electrochemical cell without any pre-treatment within 24 hours after sampling.
Results and Discussion
Surface activity of HSA
In Fig. 2 adsorption isotherms of HSA in 0.55 M NaCl and in seawater obtained at EA = -0.6 V by AC voltammetry are presented. This is the potential of electrocapillary maximum at which the surface of mercury drop has maximum surface tension and its charge is zero. Therefore, adsorption of neutral, hydrophobic molecules or their hydrophobic parts is facilitated at this potential. By increasing the concentration of protein at the electrode, double layer capacitance and measured capacitive current were decreasing. Adsorption in both electrolytes followed the Langmuir isotherm ADDIN EN.CITE Stumm199263636<style face="normal" font="default" charset="238" size="100%">Chemistry of the solid-water interface</style>[31]. In 0.55 M NaCl 2 mg dm-3 of HSA and in seawater 1.2 mg dm-3 HSA was needed to achieve complete surface coverage i . e . a d s o r p t i o n p l a t e a u ( = 1 ) . D e p e n d e n c e o f e l e c t r o d e s u r f a c e c o v e r a g e ( ) o n a d d e d H S A w a s l i n e a r i n b o t h e l e c t r o l y t e s u n t i l a b o v e m e n t i o n e d c o n c e n t r a t i o n s ( F i g . 2 B ) . F u r t h e r a d d i t i o n o f H S A u p t o 2 0 0 m g d m - 3 d i d n o t l o w e r t h e c a p a c i t i v e c u r r e n t .
C a t alytic properties of HSA
CPSA of the model protein HSA in 0.55 M NaCl and in seawater is shown in Fig. 3 By increasing the HSA concentration, CPS peak height (dE / dt)-1 was increasing until surface coverage starts to block further catalytic effect of newly adsorbed active groups. This was starting to occur at the concentration of 0.4 mg dm-3 HSA in 0.55 M NaCl (Fig. 3A). At higher concentrations number of catalytically active N atoms in solution was increasing but they could not achieve direct contact with electrode surface because it was already covered with previously adsorbed molecules. CPSA of HSA at described conditions in seawater was possible only at concentrations lower than 0.15 mg dm-3. At higher concentrations peak H was lower or two peaks appeared. The reasons could be different orientation of catalytic groups at the electrode surface and/or different availability for catalysis. Namely, as the surface coverage increases, interactions between adsorbed molecules may be expected to become significant ADDIN EN.CITE Honeychurch1996141417Honeychurch, M. J.Ridd, M. J.Honeychurch, MJ
James Cook Univ N Queensland,Dept Molec Sci,Townsville,Qld 4811,AustraliaDerivative chronopotentiometric stripping analysis of insulinElectroanalysisElectroanalysisElectroanalysisElectroanalysis4981insulinpotentiometric stripping analysisconstant current stripping analysisserum-albuminvoltammetryelectrochemistrysubstancesproteins199649-541040-0397ISI:A1996TQ09400010<Go to ISI>://A1996TQ09400010English[32]. Higher concentrations could be analysed only at more negative value of reduction current (eq. -2 or -5 A i n s t e a d o f o u r - 1 A ) w h i c h w i l l p r o v i d e l o w e r b u t r e p r o d u c i b l e p e a k H .
C P S s i g n a l s o b s e r v e d i n o u r e l e c t r o l y t e s w e r e r e s u l t o f p r e s o d i u m c a t h o d i c c a t a l y s i s o f e l e c t r o r e d u c t i o n o f h y d r o g e n i o n s . N i t r o g e n a t o m s f r o m H S A , b e a r i n g f r e e e l e c t r o n p a i r , w e r e the one that helped hydrogen ions to be reduced at the surface of mercury drop. Gaseous hydrogen was developing and peak H appeared. Its peak potential was situated at app. -1.70 V to -1.80 V, preceding the reduction of hydrogen ions on mercury without a catalyst. In general, if molecule has higher molecular mass it is catalytically more active ADDIN EN.CITE Heyrovsky200544445[17]. Therefore, N-organic polymer like HSA was a suitable compound for producing peak H in CPSA.
The height of peak H in 0.55 M NaCl and in seawater was considerably different. For example, the height of peak H in 0.55 M NaCl for 0.1 mg dm-3 HSA was 2.6 s V-1 while in seawater for the same HSA concentration the height was 15.8 s V-1. In 0.55 M NaCl the peak potential is shifted from -1.85 V to -1.78 V, while in seawater it is shifted from -1.83 V to -1.71 V, regarding the concentrations lower than 0.15 mg dm-3 (Fig. 3B). Moving of peak potential toward positive values means that the catalytic activity is favoured i.e. the process is consuming lesser amount of energy in seawater than in NaCl. The differences in catalytic properties of HSA in 0.55 M NaCl and in seawater were due to the different adsorption of HSA i.e. different composition of the electrolytes. The ionic strength of the seawater could be modelled by using the 0.55 M NaCl solution, but besides that seawater contains other macro and microconstituents, as for e.g. it contains 0.05 mol dm-3 Mg and 0.01 mol dm-3 Ca ions. They strongly influence biogeochemical processes in seawater like adsorption ADDIN EN.CITE Plavsic1998303017Plavsic, M.Cosovic, B.Plavsic, M
Rudjer Boskovic Inst, Ctr Marine & Environm Res, POB 1016, HR-10001 Zagreb, Croatia
Rudjer Boskovic Inst, Ctr Marine & Environm Res, HR-10001 Zagreb, CroatiaAdsorption of carrageenans on mercury surface in sodium chloride solution and seawaterCroatica Chemica ActaCroatica Chemica Acta233712electrodesystemsalgaeions1998233-2430011-1643ISI:000074204000004<Go to ISI>://000074204000004English[24] and complexation reactions ADDIN EN.CITE Raspor19771117<style face="normal" font="default" size="100%">Application of polarography and voltammetry to spe</style><style face="normal" font="default" charset="238" size="100%">c</style><style face="normal" font="default" size="100%">iation of trace metals in natural waters. II. Polarographic studies on the kinetics and mechanism of Cd(II)-chelate formation with EDTA in seawater</style>Thalassia JugoslavicaThalassia Jugosl.Thalassia JugoslavicaThalassia Jugosl.[33]. Stronger catalytic activity was observed in seawater (Fig. 2B) because Mg and Ca cations neutralized negatively charged groups in HSA molecule and increased the molecule's affinity toward hydrophobic mercury. Therefore, sensitivity of CPSA was enhanced in the seawater.
CPSA sensitivity - comparison with SWV and CV
Catalytic signals of HSA were also recorded with voltammetric methods SWV and CV. When compared to CPS method, these techniques have identical preconcentration step but they differ in the stripping step. SWV and CV apply the potential scanning in the negative direction ADDIN EN.CITE Kounaves199747476Handbook of Instrumental Techniques for Analytical ChemistryUpper Saddle River[29] while CPS method strips material away from the electrode by applying constant reduction current ADDIN EN.CITE Zie1992424217Zie, Y. Q.Huber, C. O.Univ Wisconsin,Dept Chem,Milwaukee,Wi 53201Constant-Current Enhanced Potentiometric Stripping AnalysisAnalytica Chimica ActaAnalytica Chimica ActaAnal. Chim. Acta632631-2potentiometrycadmiumconstant-current enhanced potentiometric stripping analysis199263-700003-2670ISI:A1992JA43900007<Go to ISI>://A1992JA43900007English[2]. If the same accumulation potential and accumulation time were applied for analysis of HSA, the results showed that constant current CPSA is a much more sensitive than both voltammetric methods. CPSA of 0.01 mg dm-3 of HSA gave well defined peak H already for 60 s of accumulation (Fig. 4C) while voltammetric methods did not give any peak even for longer accumulation times i.e. for 180 s and 300 s (Fig. 4A and 4B). Similar sensitivity results but concerning different protein solutions were reported earlier, too ADDIN EN.CITE Kizek2001181817Kizek, R.Trnkova, L.Palecek, E.Palecek, E
Acad Sci Czech Republ, Inst Biophys, Kralovopolska 135, CZ-61265 Brno, Czech Republic
Acad Sci Czech Republ, Inst Biophys, CZ-61265 Brno, Czech Republic
Masaryk Univ, Fac Sci, Dept Theoret & Phys Chem, CZ-61137 Brno, Czech RepublicDetermination of metallothionein at the femtomole level by constant current stripping chronopotentiometryAnalytical ChemistryAnalytical Chemistry48017320differential-pulse polarographycarbon electrodesrat-liverelectrochemical-behaviormercury-electrodesanimal-tissuesmetal-ionsvoltammetryproteinscadmium20014801-48070003-2700ISI:000171696800007<Go to ISI>://000171696800007English[3].
Calibration plot for HSA
As a result of the CPS method sensitivity, peak H height obtained in seawater electrolyte could be utilized for quantitative determination of N-POM in seawater samples. We observed a straight calibration line in the concentration range from 0 to 0.15 mg dm-3 of HSA (Fig. 5). That covers the range of the peak H heights of N-POM measured in seawater samples. Calibration plot is passing through the origin and it is described with the equation (dE / dt)-1 / s V-1 = 154.1 x [HSA] / mg dm-3. Inset in Fig. 4 shows the increase of the peak H height and its shift toward positive potentials with increasing HSA concentrations.
Quantitative analysis of SAS and N-POM in seawater samples from Northern Adriatic
Organic matter in seawater samples from Northern Adriatic station 101 showed surfactant activity i.e. it decreased capacitive current below the capacitive current value for pure electrolyte. For longer accumulation period the decrease is higher because more SAS is adsorbed at the electrode surface. The concentrations of SAS were expressed in equivalents of Triton-X-100 for the accumulation time of 60 s and are given in Table 1.
CPS analysis of seawater samples gave the peak at the potential around Ep ~ -1.7 V at the ascending part of the hydrogen evolution. That peak H is a consequence of the catalytic activity of N-POM present in seawater samples and it was analyzed concerning different accumulation times: 1 s, 30 s, 60 s, 120 s, 180 s and 300 s (Fig. 6) and stripping currents: 0.5 A , - 1 A , - 2 A , - 5 A , - 1 0 A a n d - 2 0 A ( n o t s h o w n ) . A s m o r e p o l y m e r i c m a t e r i a l w a s b r o u g h t t o t h e e l e c t r o d e , c a p a c i t i v e c u r r e n t w a s d e c r e a s i n g , p e a k h e i g h t a n d a r e a i n C P S A w e r e i n c r e a s i n g a n d p e a k p o t e n t i a l w a s s h i f t i n g t o w a r d p o s i t i v e v a l u e s . W i t h s h o r t a c c u m u l a t i o n t i m e s ( 1 s a n d 3 0 s ) p e a k H w a s n o t o b t a i n e d p r o b a b l e b e c a u s e t h e a m o u n t o f m a t e r i a l a d s o r b e d w a s t o l o w . S t r i p p i n g c u r r e n t s h i g h e r t h a n - 2 A a n d e q u a l o r l o w e r t o - 0 . 5 A w e r e n o t s u i t a b l e f o r m e a s u r e m e n t s a s e i t h e r n o p e a k H w a s o b t a i n e d o r t h e i r r e g u l a r i t i e s i n t h e r e c o r d e d c h r o n o p o t e n t i o g r a m w e r e t o o b i g . A c c o r d i n g t o t h e s e f i n d i n g s w e h a v e s e l e c t e d f o r a n a l y s i s o f s e a w a t e r s a m p l e s t h e a c c u m u l a t i o n t i m e 6 0 s a n d t h e s t r i p p i n g c u r r e n t o f - 1 A . C o n c e n t r a t i o n o f N - P O M w a s e x p r e s s e d i n e q u ivalent concentration of hSA (Table 1), according to the calibration plot obtained in seawater electrolyte (Fig. 4). In samples where no catalytic activity occurred we did not obtain any peak H (represented as zero in Table 1). Peak H decreased upon purging of samples with nitrogen gas. For surface sample from 6 June 2008 the peak was 76 % smaller after purging a sample for 100 s with pure nitrogen gas. In this way oxygen was purged out of the sample what caused a faster reduction of hydrogen cations and therefore lower peak H. Purging step in CPS determination of N-POM in seawater for analytical purposes influenced the results and should not be ignored.
From peak H height measured in the seawater samples we could not characterize N-POM on molecular basis, as for that some specific separation techniques and characterization methods should be included. Since monomers usually do not influence strongly the capacitive current measured at the mercury-seawater interface i.e. they have lower surface activity ADDIN EN.CITE Plavsic1994676717Plavsic, M.Cosovic, B.Plavsic, M
Ruder Boskovic Inst,Ctr Marine Res Zagreb,Pob 1016,Zagreb 41001,CroatiaAdsorption of Acrylic and Polyacrylic Acids on the Mercury-Electrode Sodium-Chloride Solution InterfaceColloids and Surfaces a-Physicochemical and Engineering AspectsColloids and Surfaces a-Physicochemical and Engineering Aspects243882-3acrylic acidadsorptionmercury electrode surfacepoly(acrylic acid)svoltammetrypulse polarographycomplexesbindingionssalt1994243-2500927-7757ISI:A1994PK37100012<Go to ISI>://A1994PK37100012English[34], we could suppose that the adsorbed polymeric organic material from seawater samples was very probably responsible for the catalytic activity. In spring/early summer and autumn in the Northern Adriatic seawater samples polysaccharides can represent significant part of the total carbon in seawater ADDIN EN.CITE DeAngelis19939917Barbarulo, M. V.Bruno, M.Volterra, L.Nicoletti, R.Deangelis, F
Univ Laquila,Dept Chem,Via Assergi 6,I-67100 Laquila,Italy
Univ Roma La Sapienza,Dept Chem,I-00185 Rome,Italy
Ist Super Sanita,Environm Hyg Lab,I-00161 Rome,ItalyChemical-Composition and Biological Origin of Dirty Sea MucilagesPhytochemistryPhytochemistryPhytochemistryPhytochemistry393342amphora-coffeaeformiscylindrotheca-fusiformispennatae diatomalgaediatomsmucilagesextracellular carbohydratespolysaccharidesmonosaccharides analysis1993393-3950031-9422ISI:A1993LY98400013<Go to ISI>://A1993LY98400013EnglishFajon1999101017Fajon, C.Cauwet, G.Lebaron, P.Terzic, S.Ahel, M.Malej, A.Mozetic, P.Turk, V.Cauwet, G
Univ Paris 06, CNRS, Observ Oceanol Banyuls, UMR 7621, F-66651 Banyuls sur Mer, France
Univ Paris 06, CNRS, Observ Oceanol Banyuls, UMR 7621, F-66651 Banyuls sur Mer, France
Ctr Marine & Environm Res, Rudjer Boskovic Inst, Zagreb 10000, Croatia
Natl Inst Biol, Marine Stn Piran, Piran 66330, SloveniaThe accumulation and release of polysaccharides by planktonic cells and the subsequent bacterial response during a controlled experimentMicrobiology Microbiology MicrobiologyMicrobiologyMicrobiologyMicrobiology351294dissolved organic matterpolysaccharidemicrocosmnutrientbacterial activityexcretiondissolved organic-carbonphytoplankton extracellular releasen-p ratiomediterranean-seaenzyme-activitydiatom bloommarine-snowphosphorusbacterioplanktonflocculation1999351-3630168-6496ISI:000081886500006<Go to ISI>://000081886500006English[21,22]. Macroaggregates found in the Northern Adriatic are characterized by high C/N ratio due to their low protein content having carbohydrates as a major component. They are mostly composed from heteropolysaccharides and polymethylene chains and originate from phytoplankton's cell walls ADDIN EN.CITE Kovac2005171717Kovac, N.Mozetic, P.Trichet, J.Defarge, C.Kovac, N
Natl Inst Biol, Marine Biol Stn, Fornace 41, Piran 6330, Slovenia
Natl Inst Biol, Marine Biol Stn, Piran 6330, Slovenia
Univ Orleans, UMR 6113 CNRS, Inst Sci Terre Orleans, F-45067 Orleans, FrancePhytoplankton composition and organic matter organization of mucous aggregates by means of light and cryo-scanning electron microscopyMarine BiologyMarine Biology2611471atomic-force microscopycoastal waters gulftransmission electronmarine snowadriatic seamicrobial sedimentsparticulate matterpolysaccharidesmucilageultrastructure2005261-2710025-3162ISI:000228974100027<Go to ISI>://000228974100027English[35]. Besides that carbohydrates are also recognized as N-containing molecules, having N mostly bound in the form of amine groups, named aminosugars ADDIN EN.CITE Benner2003161617Benner, R.Kaiser, K.Benner, R
Univ S Carolina, Dept Biol Sci, Columbia, SC 29208 USA
Univ S Carolina, Dept Biol Sci, Columbia, SC 29208 USA
Univ S Carolina, Marine Sci Program, Columbia, SC 29208 USAAbundance of amino sugars and peptidoglycan in marine particulate and dissolved organic matterLimnology and OceanographyLimnology and Oceanography118481muramic acidsea-waternitrogencarbonoceansurfacesedimentsseawaterbacteriachromatography2003118-1280024-3590ISI:000182050000011<Go to ISI>://000182050000011English[36]. Nutrients and sun light are crucial factors for phytoplankton's production/exudation of marine organic matter ADDIN EN.CITE Myklestad1995141417Myklestad, S. M.Myklestad, Sm
Univ Trondheim,Norwegian Inst Technol,Dept Biotechnol,Marine Biochem Grp,N-7034 Trondheim,NorwayRelease of Extracellular Products by Phytoplankton with Special Emphasis on PolysaccharidesScience of the Total EnvironmentScience of the Total Environment1551651-3phytoplanktonextracellular releaseextracellular polysaccharidesexcretionexudationnutrient limitationchemical structure of exudatesadriatic seasouthern north seamarine planktonic diatomsorganic-matterchaetoceros-affinishealthy cellscarbonexcretionseaphotosynthesischemistry1995155-1640048-9697ISI:A1995QV88500015<Go to ISI>://A1995QV88500015English[37]. The Adriatic Sea is in generally an oligotrophic semi-closed basin where phosphorus is a limiting nutrient. Its northern part, including station 101, is seasonally greatly influenced by terrigenous nutrient input of Po River, especially in spring and autumn because of the snow melting in Alps and frequent rains. In the surface samples from June 2008 high concentrations of SAS and N-POM were present, probable as a consequence of increased biological activity due to the early summer phytoplankton bloom occurring in the photic zone. Oppositely, at the bottom layer no peak H could be detected for 60 s accumulation and for 300 s there was only a hump (not shown), probable because OM produced at the surface has not sunken yet to the deeper layers and the old OM from previous season has been already mostly decomposed.
Concentration of N-POM expressed as eq. mg HSA dm-3 was variable through the seasons as well as SAS and DOC having the highest values in the most productive period of biological activity (June 2008) and the lowest value in the winter period (January 2009) (Table 1.). Surface water was richer in OM i.e. concentration of N-POM, SAS and DOC was higher in surface samples than in bottom samples in all seasons. To sea which part of SAS and DOC made N-POM obtained with CPSA, we calculated N-POM/SAS and N-POM/DOC and concluded that N-POM made a minor part of a few percent of SAS and DOC in seawater samples.
Conclusion
The measurement of peak H position and height by constant current CPSA was a very suitable for qualitative and quantitative determination of presodium catalysts as a part of OM pool in seawater samples. Amount of N-POM was expressed as an equivalent concentration of suitable N-containing polymer model, in our case that was protein HSA. Calibration plot of HSA obtained in OM free seawater was a straight line from 0 to 0.15 mg dm-3. Peak H strongly depends on constant stripping current applied, accumulation time as well as on catalyst concentration, its structure and basic electrolyte. The concentrations of N-POM in seawater samples from the Northern Adriatic were in the range from 0.0002 to 0.071 eq. mg HSA dm-3, being higher for surface samples in the season of increased biological production (June 2008). Concerning natural water systems, peak H represents an additional parameter for the characterization of natural organic matter in seawater measured without any sample pre-treatment. A sensitive and fast constant current CPSA is a suitable method for its analysis.
Acknowledgments
The financial support of the Croatian Ministry of Science, Education and Sport for the project no. 098-098-2934-2717 under the title The nature of the organic matter, interaction with microconstituents and surfaces in the environment is gratefully acknowledged. We also thank Zdeslav Zovko for DOC measurements in seawater samples.
References
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[12] M. Tomschik, L. Havran, M. Fojta, E. Pale r J ~
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e k , E l e c t r o a n a l y s i s 1 9 9 8 , 1 0 , 4 0 3 .
[ 1 3 ] M . H e y r o v s k y , C r o a t . C h e m . A c t a 2 0 0 6 , 7 9 , 1 .
[ 1 4 ] S . G . M a i r a n o v s k i i , C a t a l y t i c a n d K i n e t i c W a v e s i n P o l a r o g r a p h y , P l e n u m P r e s s , N e w Y o r k , 1 9 6 8 .
[ 1 5 ] B . R a s p o r , J . E l e c t r o a n a l . C h e m . 2 0 0 1 , 5 0 3 , 1 5 9 .
[ 1 6 ] A . J . B a r d , E n c y c l o p e d i a o f E l e c t r o c h e m i s t r y o f t h e E l e m e n t s , M a r c e l D e k k e r , N e w Y o r k , 1 9 7 6 .
[ 1 7 ] M . H e y r o v s k y , i n E l e c t r o c h e m i s t r y o f n u c l e i c a c i d s a n d p r o t e i n s ( E d s : E . P a l e
e k , F . S c h e l l e r , J . W a n g ) , E l s e v i e r , A m s t e r d a m , 2 0 0 5 , p p . 6 5 7 - 6 8 0 .
[ 1 8 ] J . I . H e d g e s , G . E g l i n t o n , P . G . H a t c h e r , D . L . K i r c h m a n , C . A r n o s t i , S . D e r e n n e , R . P . E v e r s h e d , I . K o g e l - K n a b n e r , J . W . d e L e e u w , R . L i t t k e , W . M i c h a e l i s , J . R u l l k o t t e r , O r g . G e o c h e m . 2 0 0 0 , 3 1 , 9 4 5 .
[ 1 9 ] J . D . P a k u l s k i , R . B e n n e r , L i m n o l . O c e a n o g r . 1 9 9 4 , 3 9 , 9 3 0 .
[ 2 0 ] K . Y . B o r s h e i m , S . M . M y k l e s t a d , J . A . S n e l i , M a r . C h e m . 1 9 9 9 , 6 3 , 2 5 5 .
[ 2 1 ] F . D e A n g e l i s , M . V . B a r b a r u l o , M . B r u n o , L . V o l t e r r a , R . N i c o l e t t i , P h y t o c h e m i s t r y 1 9 9 3 , 3 4 , 3 9 3 .
[ 2 2 ] C . F a j o n , G . C a u w e t , P . L e b a r o n , S . T e r z i c , M . A h e l , A . M a l e j , P . M o z e t i c , V . T u r k , M i c r o b i o l o g y 1 9 9 9 , 2 9 , 3 5 1 .
[ 2 3 ] I . C i g l e n e
k i , M . P l a v ai , V . V o j v o d i c , B . o s o v i , M . P e p i , F . B a l d i , M a r . E c o l . P r o g . S e r . 2 0 0 3 , 2 6 3 , 1 7 .
[ 2 4 ] M . P l a v ai , B . o s o v i , C r o a t . C h e m . A c t a 1 9 9 8 , 7 1 , 2 3 3 .
[ 2 5 ] A . J . B a r d , L . R . F a u l k n e r , E l e c t r o c h e m i c a l m e t h o d s : F u n d a m e n t a l s a n d A p p l i c a t i o n s , J o h n W i l e y a n d S o n s , N e w Y o r k , 1 9 8 0 .
[ 2 6 ] B . o s o v i , V . V o j v o d i , E l e c t r o a n a l y s i s 1 9 9 8 , 1 0 , 4 2 9 .
[ 2 7 ] M . P l a v ai , B . C o s o v i c , E l e c t r o a n a l y s i s 2 0 0 0 , 1 2 , 8 9 5 .
[ 2 8 ] B . o s o v i , P . O . L e k o , Z . K o z a r a c , E l e c t r o a n a l y s i s 2 0 0 7 , 1 9 , 2 0 7 7 .
[ 2 9 ] S . P . K o u n a v e s , H a n d b o o k o f I n s t r u m e n t a l T e c h n i q u e s f o r A n a l y t i c a l C h e m i s t r y , F . A . S e t t l e , P r e n t i c e H a l l , U p p e r S a d d l e R i v e r , 1 9 9 7 .
[ 3 0 ] W . S t u m m , J . J . M o r g a n , A q u a t i c C h e m i s t r y , J o h n W i l e y a n d S o n s , N e w Y o r k , 1 9 8 1 .
[ 3 1 ] W . S t u m m , C h e m i s t r y o f t h e s o l i d - w a t e r i n t e r f a c e , J o h n W i l e y a n d S o n s , N e w Y o r k , 1 9 9 2 .
[ 3 2 ] M . J . H o n e y c h u r c h , M . J . R i d d , E l e c t r o a n a l y s i s 1 9 9 6 , 8 , 4 9 .
[ 3 3 ] B . R a s p o r , P . V a l e n t a , H . W . N u r n b e r g , M . B r a n i c a , T h a l a s s i a J u g o s l . 1 9 7 7 , 1 3 , 7 7 .
[ 3 4 ] M . P l a v ai , B . o s o v i , 1 9 9 4 , 8 8 , 2 4 3 .
[ 3 5 ] N . K o v a
, P . M o z e t i , J . T r i c h e t , C . D e f a r g e , M a r . B i o l . 2 0 0 5 , 1 4 7 , 2 6 1 .
[ 3 6 ] R . B e n n e r , K . K a i s e r , L i m n . O c e a n o g r . 2 0 0 3 , 4 8 , 1 1 8 .
[ 3 7 ] S . M . M y k l e s t a d , S c i . T o t a l E n v i r o n . 1 9 9 5 , 1 6 5 , 1 5 5 .
T a b l e 1 . N i t r o g e n - c o n t a i n i n g p o l y m e r i c o r g a n i c m a t e r i a l ( N - P O M ) , s u r f a c e a c t i v e s u b s t a n c e s ( S A S ) , a n d d i s s o l v e d o r g a n i c c a r b o n ( D O C ) m e a s u r e d i n s e a w a t e r s a m p l e s f r o m N o r t h e r n A d r i a t i c s t a t i o n 1 0 1 . C o n d i t i o n s f o r S A S m e a s u r e m e n t s l i k e i n F i g . 2 a n d f o r N - P O M l i k e i n F i g . 3 .
d a t e o f s a m p l i n g d e p t h / m N - P O M S A S
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A d s o r p t i o n i s o t h e r m s o f H S A i n 0 . 5 5 M N a C l w i t h a d d e d 2 x 1 0 - 3 M N a H C O 3 ( p H 8 ) ( o ) a n d i n p r e c l e a n e d s e a w a t e r ( %) m e a s u r e d w i t h A C v o l t a m m e t r y w i t h o u t o f p h a s e m o d e ( f = 9 0 ) ( A ) a n d l o w e r H S A c o n c e n t r a t i o n r a n g e o f i s o t h e r m s ( B ) . C o n d i t i o n s : E A = - 0 . 6 V , t A = 6 0 s , E s = 0 . 0 1 V , a = 0 . 0 1 V .
F i g . 3
C P S A o f H S A i n 0 . 5 5 M N a C l w i t h a d d e d 2 x 1 0 - 3 M N a H C O 3 ( p H 8 ) ( o ) a n d i n p r e c l e a n e d s e a w a t e r ( %) . C o n d i t i o n s f o r A C a s i n F i g . 2 , c o n d i t i o n s f o r C P S A : E A = - 0 . 6 V , t A = 6 0 s , I = - 1 A .
F i g . 4
C V ( A ) , S W V ( B ) a n d C P S A ( C ) o f 0 . 0 1 m g d m - 3 o f H S A i n p r e c l e a n e d s e a w a t e r , a c c u m u l a t i o n t i m e : 6 0 s ( - - - - ) , 1 8 0 s ( - - - ) a n d 3 0 0 s ( - - - ) . M e a s u r e m e n t w i t h o u t a d d e d H S A ( %) . C o n d i t i o n s f o r C V : E A = - 0 . 6 V , E s = 0 . 0 1 V , v = 1 V s - 1 ; f o r S W V : E A = - 0 . 6 V , f = 1 0 0 s - 1 , a = 0 . 0 5 V , E s = 0 . 0 1 V , a n d f o r C P S A a s i n F i g . 3 .
F i g . 5
C a l i b r a t i o n l i n e f o r H S A i n p r e c l e a n e d s e a w a t e r . I n s e t : C P S s i g n a l s o f H S A , c o n c e n t r a t i o n s i n m g d m - 3 : 0 ) 0 , 1 ) 0 . 0 2 2 , 2 ) 0 . 0 3 3 , 3 ) 0 . 0 5 5 , 4 ) 0 . 0 6 6 a n d 5 ) 0 . 0 7 8 . O t h e r c o n d i t i o n s a s i n F i g . 3 .
F i g . 6
D i f f e r e n t a c c u m u l a t i o n t i m e s a p p l i e d f o r C P S A o f s e a w a t e r s a m p l e f r o m N o r t h e r n A d r i a t i c s t a t i o n 1 0 1 , d e p t h 3 1 m , s a m p l e d o n 1 7 M a r c h 2 0 0 9 . C o n d i t i o n s : E A = - 0 . 6 V , I = - 1 A , t A : 1 ) 1 s , 2 ) 3 0 s , 3 ) 6 0 s , 4 ) 1 2 0 s , 5 ) 1 8 0 s a n d 6 ) 3 0 0 s .
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