Is there future of sequential chemical extraction for speciation analysis of metal(loid)s in plants?

Figures & data

Figure 1. Publication in recent years on sequential chemical extraction (SCE) method for speciation analysis of metal(loid)s in plants.

(Source: Web of Science; Search keywords: ‘chemical forms of metal(loid)s in plant’, ‘sequential chemical extraction’).

Table 1. 6-step sequential chemical extraction (SCE) method for speciation analysis of metal(loid)s in plants [36–39].

Chemical state	Extractants	Be extracted
Ethanol extract (F1)	80% C2H5OH	Inorganic salts based on nitrates and chlorides, amino acid salts
Deionized water extraction state (F2)	Deionized water	Water-soluble organic salts, M(H2PO4)2
Sodium chloride extract (F3)	1 mol/L NaCl	Pectinate, a metal that binds to proteins or appears in the adsorbing state
Acetic acid extract (F4)	2% HAc	Phosphates that are poorly soluble in water, include M2HPO4, M3PO4
Hydrochloric acid extract (F5)	0.6 mol HCl	Oxalate
Residue form (F6)	HNO3/HClO4 (3:1 v/v)	Residue form

In this table, M only present as bivalence for convenience.

Table 2. Other sequential chemical extraction (SCE) methods for speciation analysis of metal(loid)s in plants.

Other sequential extraction methods	Extract-ants (in order of extraction)						Reference
	1	2	3	4	5	6
3-Step Method I	80% Ethanol	0.6 M hydrochloric acid	Residue, HNO3/HClO4 (3:1 v/v)				[37,38]
3-Step Method II	Deionized water	0.01 M calcium chloride	Residue, HNO3/HClO4 (3:1 v/v)				[39]
3-Step Method III	Deionized water	Hydrochloric acid HCl: = 1:3)	Residue, concentrated nitric acid				[40]
4-Step Method I	250 mL of 0.1 M potassium nitrate	0.05 M EDTA-2Na	0.01 M hydrochloric acid	Residue, HNO3/HClO4 (3:1 v/v)			[41]
4-Step Method II	95% ethanol solution	Deionized water	0.2 M hydrochloric acid	Residue, concentrated nitric acid			[42]
5-Step Method I	80% ethanol	Deionized water	1 M sodium chloride	0.6 M hydrochloric acid	Residue, HNO3/HClO4 (3:1 v/v)		[43]
6-Step Method I	80% ethanol	Deionized water	2% acetic acid	Acetone	0.5 M per chloric acid.	Residue, HNO3/HClO4 (3:1 v/v)	[44]

Table 3. Literature on sequential chemical extraction (SCE) for speciation analysis of cadmium (Cd) in plants.

Plants	Parts	Methodology	Reference
Tea, cucumber	Tea leaves, cucumber roots, stem, leaf and fruit	Ethanol extraction, hydrochloric acid extraction and residue state	[37]
Crops	Root, stem and leaf	6-Step SCE method	[9]
Chlamydomonas cyanais (Thlaspi caerulescens)	Root, Bud	Water immersion method and calcium chloride extraction method are used.	[39]
Bechmeria nivea (L.) Gaud.	Root, stem, leaf	6-Step SCE method	[45]
Phytolacca americana L.	Root, stem, leaf	6-Step SCE method	[46]
Rice	Roots, above ground	6-Step SCE method	[47]
Bougainvillea spectabilis Willd	leaf	6-Step SCE method	[48]
Watercress (Nasturtium officinale L. R. Br.)	Roots, branches	6-Step SCE method	[49]
Lettuce (Lactuca sativa L.)	leaf	6-Step SCE method	[50]
Tobacco	Roots, leaves	6-Step SCE method	[51]
Festuca arundinacea	Roots, leaves	6-Step SCE method	[52]
Winter wheat (Triticum aestivum)		6-Step SCE method	[53]
Solanum nigrum	Root, stem, leaf	6-Step SCE method	[54]
Amaranthus hybridus L.	leaves	6-Step SCE method	[55]
Myriophyllum aquaticum	Leaf, stem	6-Step SCE method	[56]
Ryegrass	Roots, leaves	6-Step SCE method	[57]
Spinach	roots, sprouts	6-Step SCE method	[58]
Chili pepper	Fruit	6-Step SCE method	[59]
Zea mays	Root, Bud	6-Step SCE method	[60]
Hydrilla verticillata	Root, stem, leaf	6-Step SCE method	[61]
Salix	Root, stem, leaf	6-Step SCE method	[62]
Triarrhena sacchariflora (Maxim.) Nakai. seedlings	Leaves	6-Step SCE method	[63]
Koelreuteria paniculata	Roots, stem, leaves	6-Step SCE method	[64]
Arabidopsis thaliana	Roots	6-Step SCE method	[65]
Dwarf polish wheat (Triticum polonicum L.)	Root, Bud	6-Step SCE method	[66]
Peanut	Roots, leaves	6-Step SCE method	[67]
Morus alba L.	Root, stem, Leaf	6-Step SCE method	[68]
Duckweed (Lemna minor L.)	Root	Ethanol extraction, hydrochloric acid extraction, residual state	[38]
Radish cultivars (Raphanus sativus L.)	Roots, Leaves	6-Step SCE method	[69]
Wild Mugwort, red thistle and artemisia	Root, stem, leaf	6-Step SCE method	[70]
Brassica napus	Roots, leaves	6-Step SCE method	[71]
Soybean	Root	6-Step SCE method	[72]
Cattails	Root	6-Step SCE method	[73]
Impatiens walleriana	Root, stem, leaf	6-Step SCE method	[65]
dark septate endophyte (DSE), Exophiala pisciphila		6-Step SCE method	[74]
Sesuvium portulacastrum		6-Step SCE method	[75]
Potato	Root, stem, leaves, fruit (tuber)	6-Step SCE method	[76]
Tomato	fruit	6-Step SCE method	[77]
Echinodorus osiris Rataj	Root, stalk, leaf	6-Step SCE method	[78]
Barley	Roots, Above ground parts	6-Step SCE method	[79]
Pansy	Overground, Underground	6-Step SCE method	[80]
Kentucky bluegrass and tall fescue	Roots, Leaves	6-Step SCE method	[81]
Strawberry	Aboveground part	6-Step SCE method	[82]
Medicago sativa L.	Root, Bud	6-Step SCE method	[83]
Chardonnay seedlings	Fine root, thick root	6-Step SCE method	[84]
Chinese cabbage (Brassica parachinensis L.)	Root, Bud	6-Step SCE method	[85]
Marigold	Root, stem, leaf	6-Step SCE method	[86]
Salix officinalis	Roots, leaves	6-Step SCE method	[87]
Sedum	Root, stem, leaf	6-Step SCE method	[88]
Miscanthus floridulus	Root, stem, leaf	6-Step SCE method	[89]
Typha latifolia L.	Root, Rhizomes, leaves	6-Step SCE method	[90]
Potentilla villosa	Leaf blade, petiole, root	6-Step SCE method	[91]
Ligusticum chuanxiong	Leaves, stem or roots	6-Step SCE method	[92]
Rape	Leaves, stem	6-Step SCE method	[93]
Salix matsudana	Roots, leaves, stem	6-Step SCE method	[94]
Duckweed	Leaves, stems	6-Step SCE method	[95]
Amaranth (Amaranthus tricolor L.)	Roots, stems, and leaves	6-Step SCE method	[96]
Maize	Roots, stems,	6-Step SCE method	[97]
Rice	Roots, stems, and leaves	6-Step SCE method	[98,99]
Vegetable Crops	Roots, stems,	6-Step SCE method	[100]
Wheat (Triticum polonicum L.)	Roots, stems,	6-Step SCE method	[99,101]
Rice	Rice straw,	4-Step SCE method	[102]
Barley	Leaves	6-Step SCE method	[103]
Chinese goldthread	Leaves, rhizomes, and roots	6-Step SCE method	[104]
Arabidopsis halleri ssp. gemmifera	Roots, stems, and leaves	6-Step SCE method	[105]
Rape	Rape straw	4-Step SCE method	[106]

Table 4. Literature on sequential chemical extraction (SCE) for speciation analysis of lead (Pb), copper (Cu) and zinc (Zn) in plants.

Plants	Parts	Metal	Methodology	Reference
Crops, soybean		Pb, Cu	6-Step SCE method	[9,23]
Rice, wheat seeds	Roots, stems, leaves	Pb,Cu,Zn	6-Step SCE method	[107,108]
Maize	Root, Stem, leaf	Pb, Cu, Zn	6-Step SCE method	[109,110]
Lettuce	leaves	Pb,Cu	6-Step SCE method	[50,111]
Wild Mugwort, red Thistle and artemisia	Root, Stem, leaf	Pb, Zn	6-Step SCE method	[70]
Oleander, luan, Paulownia and ramie	Root, Stem, leaf	Pb, Zn	6-Step SCE method	[112]
Potentilla villosa	Leaf blade, petiole, root	Pb, Zn	6-Step SCE method	[113,114]
Lolium perenne	bud	Pb	6-Step SCE method	[115]
Tea plant	Root	Pb	6-Step SCE method	[116]
Porphyra yezoensis		Pb	6-Step SCE method	[117]
Duckweed (Landoltia punctata)		Pb	6-Step SCE method	[118]
Spirodela polyrhiza (L.)	leaves	Pb	6-Step SCE method	[119]
Sugar cane	Roots, leaves	Pb	6-Step SCE method	[120]
Salix	Root, Stem, leaf	Pb	6-Step SCE method	[62]
Robinia pseudoacacia L.	Root, Stem, leaf	Pb	6-Step SCE method	[121]
Eupatorium adenophorum	Root, Stem, leaf	Pb	6-Step SCE method	[122]
Athyrium wardii	Root, Bud	Pb	6-Step SCE method	[123]
Arenaria orbiculata		Pb	6-Step SCE method	[124]
Platycladus orientalis	leaves	Pb	6-Step SCE method	[125]
Wheat, maize	Root, leaves	Pb	6-Step SCE method	[126]
Salsola passerina Bunge and Chenopodium album L.	Root, Stem	Pb	80% ethanol and 2% acetic acid, deionized water, 0.6 mol/L hydrochloric acid, 1 mol/L sodium chloride solution	[127]
Apple tree	Roots	Cu	6-Step SCE method	[128]
Brassica napus	Roots, leaves	Cu	6-Step SCE method	[71]
Soybean	Roots	Cu	6-Step SCE method	[72]
Tomato seedlings	Root, stem, leaves	Cu	6-Step SCE method	[129]
Seaweed	Root, stem, leaf	Cu	6-Step SCE method	[130]
Commelina communis	Root, stem, leaf	Cu	6-Step SCE method	[131]
Thlaspi caerulescens	Roots, leaves	Zn	Water immersion method and calcium chloride extraction method are used	[39]
Sedum	Roots, stems, leaves	Zn	6-Step SCE method	[132]
Potentilla （Potentilla griffithii var. velutina）	Leaves, petioles, roots	Zn	6-Step SCE method	[133]
Porphyra yezoensis	Leaves, stem	Pb	6-Step SCE method	[134]
Rape	Leaves, stem	Zn	6-Step SCE method	[93]
Pakchoi, Radish and Chili	Root, stem, leaves	Pb	4-Step SCE method	[135]
Rape	Rape straw	Pb, Cu, Zn	4-Step SCE method	[106]

Table 5. Literature on sequential chemical extraction (SCE) for speciation analysis of calcium (Ca) and manganese (Mn) in plants.

Plants	Parts	Metal	Methodology	Reference
Pear	pulp	Ca	6-Step SCE method	[136]
Rice	Roots, stems, leaves	Ca	6-Step SCE method	[108]
Sagittaria sagittifolia	Roots, main stems, bulbs	Ca	6-Step SCE method	[137]
Radish leaves, Cabbage	Aboveground part	Ca	Deionized water, hydrochloric acid (HCl: H2O = 1:3) and concentrated nitric acid give soluble free, inorganic, and organic aluminum, respectively.	[40]
Amaranth (Amaranthus tricolor L.)	Roots, stems, leaves	Ca	6-Step SCE method	[96]
Turnip		Ca	6-Step SCE method	[138]
Tea, Cucumber	Tea, cucumber roots, stems, leaves and fruits	Mn	Ethanol extraction, hydrochloric acid extraction and residue state	[37]
Xanthium strumarium L.	leaf	Mn	6-Step SCE method	[139]
Cleome viscosa L.	Roots, stems, leaves	Mn	6-Step SCE method	[140]
Macleaya cordata (Papaveraceae)	Leaves, stems, roots	Mn	6-Step SCE method	[141]
Soybean seedlings	root	Mn	6-Step SCE method	[23]
Paulownia, Bamboo, Peach, Koelreuteria	Roots, stems, leaves	Mn	6-Step SCE method	[142]
Rape	Rape straw	Mn	4-Step SCE method	[106,143]

Figure 2. The chemical forms of metals in various environmental matrices..

Table 6. Phosphate solubility product of some metal elements.

Phosphate	KSP	Ref
Cd3(PO4)2	3 × 10 − 33	[152]
Ca3(PO4)2	2.07 × 10 − 33	[162]
Cu3(PO4)2	1.3 × 10 − 37	[163]
Mg3(PO4)2	6 × 10 − 26	[162]
Pb3(PO4)2	8 × 10 − 43	[153]
CrPO4	1.0 × 10 − 17	[155]
Ag3PO4	1.6 × 10 − 16	[164–181]
GdPO4	1.4 × 10 − 26	[154]

Table 7. Literature on sequential chemical extraction (SCE) for speciation analysis of non-bivalent metals in plants.

Metals	Plant	Parts	Method	Reference
Chromium (Cr^3+)	mushroom	roots, stems, leaves	6-Step SCE method	[39]
	Rice	roots, stems, leaves	6-Step SCE method	[159]
Silver (Ag^+)	Lettuce	leaf	6-Step SCE method	[182]
Antimony (Sb(V))	Banyan Tree		6-Step SCE method	[156]
Aluminium (Al^3+)	Corn	root	The roots were magnetized and stirred in 250 mL of 0.1 M potassium nitrate, 0.05 M EDTA-2Na and 0.01 M HCl solution for 1 h, and exchangeable aluminium, complexed aluminium and precipitated aluminium were extracted, respectively. Finally, rinse twice with distilled water, dry at 80°C, and digest with concentrated nitric acid to determine residual aluminium.	[41]
Arsenic (As(V))	Radish leaves, Cabbage, Eucalyptus	Aboveground part	Deionized water, hydrochloric acid (HCl: = 1:3) and concentrated nitric acid give soluble free, inorganic, and organic aluminium, respectively.	[40]
	Eucalyptus		6-Step SCE method	[157]
Gadolinium (Gd^3+)	Rice seedlings	bud	6-Step SCE method	[185]
Cerium (Ce^3+)	Rice seedlings	Roots, shoots	6-Step SCE method	[186]
Yttrium (Y^3+)	Rice seedlings	Roots, shoots	6-Step SCE method	[187]

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