. 2014 Apr 30;2:19. doi: 10.3389/fchem.2014.00019

Table 2.

Summary of analytical performances and experimental conditions obtained for heavy metals detection in French scientific academic community.

Classification	References	Electrochemical platform	Detection medium	Technique	Analyte(s)	LOD	Linear concentration range	Analyte pretreatment conditions
POLAROGRAPHY
			Online monitoring river	DPASV	Total Zn	2.91 nM	12.4–23.2 nM	30 s at −1.3V
				DPASV	Total Pb	0.03 nM	1.7–3.2 nM	60 s at −0.7V
	Magnier et al., 2011	HMDE		DPCSV	Total Cu	0.6 nM	4.9–7.6 nM	30 s at −1.1 V followed by an adsorption step at −0.25 V during 15 s
	Riso et al., 2006	HgFE	Water samples (treated)	SCP	Fe(III)	1.5 nM	NC	6 cycles of: 0.04 V (9 s) and −0.4V (1 s)
	Tanguy et al., 2010	HgFE	Seawater samples (treated)	SCP	Sb(III)	70 pM	depending on sample	300 s at −0.45 V
	Sladkov et al., 2003	HgFE	0.1 M HNO₃	SWCSV	Se(IV)	0.8 nM	1–1000 nM	300 s at −0.45 V
	Riso et al., 1997	HgFE	Seawater	SCP	Cu	0.7 nM	NC	15 min at −1.1 V
					Pb	14 pM
					Cd	9 pM
	Cugnet et al., 2009	SPμEAs	0.2 M acetate (pH = 4.5)	SWASV	Cd(II)	11.6 nM	11.6–89 nM	300 s at −1 V
	Parat et al., 2011a	HMDE	0.1 M KNO₃	AGNES-SCP	Zn²⁺	4 nM	at least 25–100 nM	1400 s total with complex procedure
					Cd²⁺	2.9 nM
					Pb²⁺	4.1 nM
	Parat et al., 2007	Membrane and Hg film SPE	0.2 M acetate (pH = 4–7)	SWASV	Cd(II)	2 nM	5–100 nM	60 s at −1 V
	Munteanu et al., 2009	Mercury monolayer carbon fiber electrode	NC	SWASV	Pb(II)	80 fM	1–10 pM	1 s at −1.2 V
	Parat et al., 2011b	Hg film SPE	0.2 M acetate (pH = 4.6)	SSCP	Cd	2.2 nM	NC	60 s at −1 V
	Zaouak et al., 2010a	Hg film SPE	0.2 M acetate (pH = 4.5)	SWASV	Cd	1.78 nM	1.78–356 nM	60 s at −1 V
Bi FILMS
	Guo et al., 2005	GC/BiFE	Milk vetch in 0.2 M KSCN	ASV	Zn(II)	9.6 nM	500–3000 nM	120 s at −1.4 V
	Legeai et al., 2005	GC/BiFE	0.125 M HNO₃ + 0.04 M H₂NSO₃H	DPASV	Cd(II)	~10 nM	20–1000 nM	1200 s at −0.95 V
	Legeai et al., 2006	Cu/Bi film electrode	0.01 M ammonia buffer (pH = 9)	SWASV	Ni²⁺	NC	10–1000 nM	900 s at −0.7 V
	Legeai and Vittori, 2006	Cu/Nafion/Bi electrode	0.01 M NaCl + 0.001 M NaHCO₃	DPASV	Cd²⁺	6.05 nM	17.8–107 nM	300 s at −0.95V
	Legeai and Vittori, 2006	Cu/Nafion/Bi electrode	0.01 M NaCl + 0.001 M NaHCO₃	DPASV	Pb²⁺	3 nM	9.65–86.9 nM	300 s at −0.95V
	Urbanova et al., 2010	Highly porous Bi film electrodes	0.1 M acetate buffer (pH = 4.5)	DPASV	Cd(II)	5.34 nM	178–1160 nM	90 s at −0.95 V
	Urbanova et al., 2010	Highly porous Bi film electrodes	0.1 M acetate buffer (pH = 4.5)	DPASV	Pb(II)	6.27 nM	96.5–627 nM	90 s at −0.95 V
	Zaouak et al., 2009	Bi-Coated SPμE	0.2 M acetate buffer (pH = 4.5)	SWASV	Cd(II)	11.6 nM	45–400 nM	120 s at −1 V
	Lu et al., 2010	Bi doped carbon SPE	Air	SWASV	Pb(II) as vapor	1 ng	10–80 ng	120 s at −1.2 V
CARBON ELECTRODE MATERIALS
DLC/GC
	Feier et al., 2012	Graphite felt	0.1 M NaBF₄	LSASV	Zn(II)	50 nM	1–100 μM	300 s at −1.4 V
	Nasraoui et al., 2009	Graphite felt	0.1 M LiClO₄	LSASV	Pb(II)	1 nM	10–500 nM	300 s at −1 V
	Khadro et al., 2009	GC electrode	0.1 M HCl	DPASV	Ni(II)	2.56 nM	8.52–9370 nM	60 s at −1 V
	Khadro et al., 2009	GC electrode	0.1 M acetic buffer	DPASV	Hg(II)	0.15 nM	0.5–1740 nM	60 s at −1 V
	Khadro et al., 2011	B-doped DLC	Acetate (pH = 4.2)	SWASV	Cd(II)	4.83 nM	4.83–121 nM	90 s at −1.3 V
					Pb(II)	8.9 nM	8.9–222 nM
					Ni(II)	34.1 nM	34.1–256 nM
					Hg(II)	4.99 nM	5–125 nM
BDD
	Le et al., 2012	BDD	acetate pH = 5.2	SWASV	Pb(II)	19.3 nM	96.5–480 nM	600 s at −1 V
	El Tall et al., 2007	BDD	0.01 M acetate	DPASV	Cu(II)	14.2 nM	47–315 nM	60 s at −1.9 V
					Pb(II)	5.55 nM	18–217 nM
					Zn(II)	25.5 nM	77–305 nM
					Cd(II)	3.2 nM	11–222 nM
	Sbartai et al., 2012	BDD	Potassium citrate / HCl	DPASV	Cd(II)	3.29 nM	NF	20 s at −1.7 V
					Pb(II)	26.5 nM
					Ni(II)	116 nM
					Hg(II)	11.5 nM
ISEs
CALIXARENE
	Yaftian et al., 2006	Calix[4]arene	Complex (pH = 3.5–5)	SCP	Pb(II)	1.4 μM	10μM–10 mM	No accumulation and electrolysis
	Yaftian et al., 2007	Calix[4]arene	Complex (pH = 3–7)	SCP	Pb(II)	4 nM	10 nM–100 μM	No accumulation and electrolysis
CHALCOGENIDE
	Cali et al., 2002	Cu-As-S	KNO₃	SCP	Cu(II)	1 μM	2 μM–10 mM	No accumulation and electrolysis
	Essi and Pradel, 2011a,b	Cu-Ag-S	Complex (pH = 3–5)	SCP	Cu(II)	1 μM	NC	No accumulation and electrolysis
	Mear et al., 2005	Ge₂₈Se₆₀Sb₁₂	KNO₃ (pH = 3)	SCP	Cd(II)	1 μM	1 μM–10 mM	No accumulation and electrolysis
CMEs
MINERALS
	Walcarius et al., 1999a	Silica modified CPE	0.2 M HNO₃	SWASV	Cu(II)	2 nM	5 nM–5 μM	600 s accumulation followed by 30 s at −0.5 V
	Walcarius et al., 2000	Silica-modified electrode	0.1 M HNO₃	SWASV	Hg(II)	50 nM	200 nM–10 μM	600 s accumulation at open circuit followed by 60 s at −0.5 V
	Walcarius et al., 1999b	Several silica/hybrid CPE with amine functionalization	0.05 M acetic acid + 0.05 M NaNO₃	LSASV	Cu(II)	NC	unclear	Several accumulation time and 240 s at −0.4 V
	Etienne et al., 2001	Organically modified silica	0.1 M sodium acetate	SWASV	Cu(II)	3 nM	50–200 nM	60 s at −0.5 V
	Sayen et al., 2003	Carnosine silica hybrid material modified CPE	0.1 M NaNO₃ + 0.01 M HNO₃	DPASV	Cu(II)	4 nM	50–1000 nM	90 s at −0.5 V
	Walcarius and Sibottier, 2005	Amine-functionalized porous silica films on Au	0.1 M HNO₃ + 0.1 M NaNO₃ in 95% ethanol	DPASV	Cu(II)	40 nM	0.1–10 μM	600 s accumulation followed by 60 s at −0.4 V
	Etienne et al., 2007	Surfactant-templated thiol-functionalized silica thin films	0.5 M HCl	DPASV	Ag(I)	6 nM	0.2–10 μM	960 s accumulation followed by 60 s at −0.6 V
	Sanchez and Walcarius, 2010	GC/MTTZ	0.1 M HCl	SWASV	Hg(II)	2 nM	50 nM–1 μM	300 s at −0.4 V
	Walcarius et al., 1998	Mesoporous pure silica modified carbon paste electrode	0.2 M HNO₃	SWASV (or CV for larger amounts)	Cu(II)	30 nM	NC	300 s accumulation followed by 60 s at −0.5 V
	Walcarius et al., 1998	Mesoporous pure silica modified carbon paste electrode	0.2 M HNO₃	SWASV (or CV for larger amounts)	Hg(II)	50 nM	NC	300 s accumulation followed by 60 s at −0.5 V
	Tonle et al., 2005	Clays grafted with organic chelating groups (thiol or amine) modified CPE	0.1 M HNO₃	DPASV	Hg(II)	68 nM (thiol) 87 nM (amine)	100–700 nM	180 s accumulation followed by 60 s at −0.4 V (or −0.6 V depending on the medium)
	Tonle et al., 2011	Thiol-functionalized clay modified CPE	0.2 M HNO₃	SWASV	Pb(II)	60 nM	0.3–10 μM	600 s accumulation followed by 60 s at −0.9 V
	Tchinda et al., 2007	GC/PCH-SH	0.1 M HCl + 5% thiourea	DPASV	Hg(II)	0.4 nM	4–20 nM and 50–80 nM	1200 s accumulation followed by 180 s at −0.7 V
MACROCYCLIC COMPOUNDS
	Rouis et al., 2013	β-ketoimine calix[4]arene on ITO	0.05 M ammonium acetate (pH = 7)	Impedance	Hg²⁺	NC	0.1 nM–0.5 μM
	Goubert-Renaudin et al., 2009a	Cyclam-functionalized silica CPE	3 M HNO₃	SWASV	Cu(II)	0.8 nM	2–100 μM	1800 s accumulation followed by 60 s at −0.5V
	Goubert-Renaudin et al., 2009b	(TETAM) grafted to silica gel and ordered mesoporous silica	0.1 M ammonium acetate buffer (pH = 7)	SWASV	Pb(II)	2.7 nM	10–100 nM	900 s accumulation followed by 60 s at −0.8 V
	Nasraoui et al., 2010a	TETRAM-modified graphite felt electrode	0.1 M aqueous solution of LiClO₄	LSASV	Pb(II)	25 nM	100–250 nM	around 1800 s accumulation followed by 300 s at −1 V
	Nasraoui et al., 2010b	Cyclam-modified graphite felt	0.5 M H₂SO₄	LSASV	Pb(II)	25 nM		several accumulation time followed by 300 s at −1 V
	Parat et al., 2006	Hg film modified SPE	0.1 M KNO₃	LSASV	Cd(II)	6 nM	NC	120 s at −1 V
	Parat et al., 2006	Hg film modified SPE	0.1 M KNO₃	LSASV	Pb(II)	8 nM	NC	120 s at −1 V
	Betelu et al., 2007	Hg film + membrane modified SPE	0.01 M NaHCO₃	LSASV	Cd(II)	NC	NC	120 s at −1 V
	Betelu et al., 2007	Hg film + membrane modified SPE	0.01 M NaHCO₃	LSASV	Pb(II)	NC	NC	120 s at −1 V
POLYMERS
	Heitzmann et al., 2007	Poly(pyrrole-EDTA like) film	0.1 M buffer (pH = 5)	SWASV	Cd(II), Pb(II) and Cu(II)	NC	NC	600 s accumulation followed by 40 s at −1.2 V for Pb(II) and −0.9 V for Cu(II)
					Hg(II)	0.5 nM	NC
	Buica et al., 2009a	Poly(EDTA-like) Film	0.1 M acetate buffer (pH = 4.5)	DPASV	Cu(II)	0.5 nM	NC	600 s accumulation followed by 60 s at −0.4 V
	Buica et al., 2009b	Poly(pyrrole-EDTA) modified electrode	0.1 M acetate buffer (pH = 4.5)	DPASV	Hg(II)	10 nM (imprinted polymers)	10–1000 nM (imprinted polymers)	600 s accumulation followed by 180 s at −1.8 V
					Pb(II)	0.5 nM	10–1000 nM	600 s accumulation followed by 40 s at −0.9 V
					Cu(II)	5 nM	25–250 nM
	Heitzmann et al., 2005	Poly(pyrrole-malonic acid) film modified carbon electrode	0.2 M acetate buffer (pH = 4.4)	SWASV	Hg(II)	50 nM	NC
	Heitzmann et al., 2005	Poly(pyrrole-malonic acid) film modified carbon electrode	0.2 M acetate buffer (pH = 4.4)	SWASV	Cd(II)	0.2 μM	1–10 μM	600 s accumulation followed by 40 s at −1.1 V
	Pereira et al., 2011	Complexing polymer films	0.1 M acetate buffer (pH = 4.4)	SWASV	Pb(II)	0.5 nM	10–1000 nM	600 s accumulation followed by 40 s at −0.9 V or −1.1 V for Cd(II)
					Cu(II)	5 nM	25–250 nM
					Hg(II)	100 nM	100–1000 nM
					Cd(II)	500 nM	100–10000 nM
	Rivas et al., 2006	Complexing polymer films	0.1 M acetate buffer (pH = 4.8)	SWASV	Pb(II)	NC	0.01–5 mM	600 s accumulation followed by 40 s at −0.6 V
	Bessbousse et al., 2011	Nanoporous β-PVDF membrane electrode	0.1 M sodium acetate	SWASV	Pb(II)	0.63 nM	NC	30 min equilibrium followed by 100 s at −0.8 V
	Zejli et al., 2007	Polythiophene film	0.2 M KNO₃ (pH = 5)	DPASV	Ag(I)	0.56 μM	0.65–9.3 μM	120 s at −0.5 V
	Yasri et al., 2011	GC/PEDOT:PSS	HCl (pH = 2.2)	CA	Pb(II)	0.19 nM	2–100 nM	30 s at −0.65 V
NPs
	Ottakam Thotiyl et al., 2012	Au/MPS-(PDDA-AuNPs)	Phosphate buffer (pH = 8)	DPASV	As(III)	0.48 μM	NC
	Hezard et al., 2012a	GC + AuNPs	0.01 M HCl	SWASV	Hg(II)	0.42 nM	0.64–4 nM	300 s at 0 V
	Hezard et al., 2012b	GC + AuNPs	0.01M HCl	SWASV	Hg(II)	0.4 nM	0.8–9.9 nM	300 s at 0 V
BIOSENSORS
	Chouteau et al., 2004	Alkaline phosphatase	10 mM Tris-HCl buffer (pH = 8.5) / 1 mM MgCl₂	Conductometry	Cd²⁺	8.9 nM	NC
	Chouteau et al., 2005	Alkaline phosphatase Acetylcholinesterase	10 mM Tris-HCl buffer (pH = 8.5) / 1 mM MgCl₂	Conductometry	Cd²⁺	89 nM	NC	30 min incubation
	Chouteau et al., 2005	Alkaline phosphatase Acetylcholinesterase	10 mM Tris-HCl buffer (pH = 8.5) / 1 mM MgCl₂	Conductometry	Zn²⁺	0.15 μM	NC	30 min incubation
	Tekaya et al., 2013	Alkaline phosphatase	5 mM HEPES buffer (pH = 8.1)	Conductometry	Cd²⁺	10⁻²⁰ M	NC	24 h incubation
					Hg²⁺
	Soldatkin et al., 2012	Invertase, mutarotase, glucose oxidase	5 mM phosphate buffer (pH = 6.5)	Conductometry	Hg²⁺	25 nM	NC	20 min incubation
					Ag⁺	100 nM
	Mohammadi et al., 2005	Invertase, mutarotase, glucose oxidase	0.1 M phosphate buffer (pH = 6)	Amperometry	Hg(II)	NC	10 nM–1 μM	20 min incubation at pH = 4
	Gayet et al., 1993	L-lactate dehydrogenase L-lactate oxidase	0.1 M Tris buffer (pH = 9)	Amperometry	Hg(II)	1 μM	NC	5 min incubation
					Ag⁺	0.1 μM
					Cd²⁺	10 μM
					Zn²⁺	10 μM
					Pb²⁺	50 μM
					Cu²⁺	250 μM

^*All parameters given are the ones for the best LODs.