Fig. 1 pH and electrical conductivity (EC) in leachates from Technosols with gossan and/or sulfide wastes (Mean ± SD; n = 3 or 4 depending on assay). Values from same assay and
sampling period followed by a different letter are significantly different (p < 0.05) ... 216 Fig. 2 Concentrations of cations in leachates from Technosols and gossan wastes – assay 1
(Mean ± SD; n = 3). Values from same sampling period followed by a different letter are
Índice de figuras
significantly different (p < 0.05)... 218 Fig. 3 Dehydrogenase activity in mine wastes and Technosols materials from the three
assays (Mean ± SD; n = 3). Values from same assay and sampling period followed by a
different letter are significantly different (p < 0.05)... 221 Fig. 4 Acid phosphatase and -glucosidase activity in mine wastes and Technosols materials
from the three assays (Mean ± SD; n = 3). Values from same assay and sampling period
followed by a different letter are significantly different (p < 0.05)... 222 Fig. 5 Concentrations of cations in leachates from Technosols and sulfide wastes – assay 2
(Mean ± SD; n = 4). Values from same sampling period followed by a different letter are
significantly different (p < 0.05)... 225 Fig. 6 Concentrations of cations in leachates from Technosols and sulfide wastes – assay 2
(Mean ± SD; n = 4). Values from same sampling period followed by a different letter are
significantly different (p < 0.05)... 228 Fig. 7 Concentrations of cations in leachates from the overlapping of two Technosols or two
mine wastes – assay 3 (Mean ± SD; n = 4). Values from same sampling period followed by a
different letter are significantly different (p < 0.05)... 230 9. IMPROVEMENT OF CHEMICAL AND BIOLOGICAL PROPERTIES OF GOSSAN MINE WASTES FOLLOWING APPLICATION OF AMENDMENTS AND GROWTH OF CISTUS LADANIFER L.
Fig. 1 Effects of treatments (control and gossan wastes with amendment application at 30, 75 and 150 Mg/ha) and presence of Cistus ladanifer on the concentration of chemical elements in the available fraction of gossan wastes at the beginning (after 15 days of incubation and before sowing) and end of the experiment (505 days after sowing) (Mean ± SD; n = 3). Values followed by a different letter are significantly different (p < 0.05), small letters indicate comparisons between treatments from the same sampling date and capital letters indicate
comparisons between treatments in different dates and with or without plants.. 248 Fig. 2 Effects of treatments (control and gossan wastes with amendment application at 30, 75
and 150 Mg/ha) and presence of Cistus ladanifer on enzymatic activities at the beginning (after 15 days of incubation and before sowing) and end of the experiment (505 days after sowing) (Mean ± SD; n = 3). Values followed by a different letter are significantly different (p <
0.05), small letters indicate comparisons between treatments from the same sampling date and capital letters indicate comparisons between treatments in different dates and with or
without plants... 250 10. COMBINED REHABILITATION OF GOSSAN AND SULFIDE-RICH WASTES BY PHYTOSTABILISATION WITH AUTOCHTHONES SPECIES USING TECHNOSOLS
Fig. 1 Scheme of the combined rehabilitation system... 265 Fig. 2 Effects of treatments (gossan wastes and Technosols) on the concentration of the
elements in the available fraction at the beginning (after one month of incubation) and end of the assay with Lavandula pedunculata (after one year of plants growth) (mean ± SD; n = 4).
Values from same sampling period followed by a different letter are significantly different (p <
0.05)….………..……….. 273 Fig. 3 Effects of treatments (gossan wastes and Technosols) on the concentration of the
elements in the available fraction at the beginning (after one month of incubation) and end of the assay with Cistus ladanifer (after three years of plants growth) (mean ± SD; n = 4). Values from same sampling period followed by a different letter are significantly different (p <
0.05)………...……….. 274
Fig. 4 Effects of the Technosols on the concentration of the potentially hazardous elements in the roots and shoots of Lavandula pedunculata and Cistus ladanifer. Values from same
species, organ and element followed by a different letter are significantly different (p < 0.05).. 278 Fig. 5 Effects of the Technosols on the concentration of macronutrients in the roots and
shoots of Lavandula pedunculata. Values from same organ and element followed by a
different letter are significantly different (p < 0.05)... 280 Fig. 6 Effects of the Technosols on the concentration of micronutrients in the roots and shoots
of Lavandula pedunculata. Values from same organ and element followed by a different letter
are significantly different (p < 0.05)... 281 Fig. 7 Effects of the Technosols on the concentration of macronutrients in the roots and
shoots of Cistus ladanifer. Values from same organ and element followed by a different letter
are significantly different (p < 0.05)... 282 Fig. 8 Effects of the Technosols on the concentration of micronutrients in the roots and shoots
of Cistus ladanifer. Values from same organ and element followed by a different letter are
significantly different (p < 0.05)... 283 11. EVALUATION OF CHEMICAL PARAMETERS AND ECOTOXICITY OF A SOIL DEVELOPED ON GOSSAN FOLLOWING APPLICATION OF POLYACRYLATES AND GROWTH OF SPERGULARIA PURPUREA
Fig. 1 Values of pH and electrical conductivity (EC) in simulated leachates (DIN extraction) and pore water solution from initial soil and soils from treatments of the mesocosm assay (control; soils amended with diapers, polymer from diapers and synthetic polymer 7015).
Different letters in the same parameter and extractable solution indicate significant differences
(p < 0.05)... 305 Fig. 2 Cation concentrations in simulated leachates (DIN extraction) and pore water solution
from initial soil and soils from treatments of the mesocosm assay (control; soils amended with diapers, polymer from diapers and synthetic polymer 7015). Different letters in the same
parameter and extractable solution indicate significant differences (p < 0.05)……….………….. 306 Fig. 3 Anions concentrations in simulated leachates (DIN extraction) and pore water solution
from initial soil and soils from treatments of the mesocosm assay (control; soils amended with diapers, polymer from diapers and synthetic polymer 7015). Different letters in the same
parameter and extractable solution indicate significant differences (p < 0.05)……….………….. 307 Fig. 4 Chemical elements concentrations in simulated rizosphere solution, extracted with an
organic acid solution, from initial soil and soils from treatments of the mesocosm assay
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(control; soils amended with diapers, polymer from diapers and synthetic polymer 7015).
Different letters indicate significant differences (p < 0.05)……….…. 308 Fig. 5 Percentage of immobilisation of Dapnhia magna - acute toxicity test of soil leachates
from initial soil and soils from treatments of the mesocosm assay (control; soils amended with diapers, polymer from diapers and synthetic polymer 7015). Different letters indicate
significant differences (p < 0.05)... 314 Fig. 6 Growth inhibition percentage of microalgae - toxicity test with soil leachates from initial
soil and soils from treatments of the mesocosm assay (control; soils amended with diapers, polymer from diapers and synthetic polymer 7015). Different letters indicate significant
differences (p < 0.05)... 314 12. CONCLUSÕES GERAIS
ÍNDICE DE QUADROS
1. REVISÃO BIBLIOGRÁFICA
Quadro 1 Características químicas da drenagem ácida de algumas minas da Península
Ibérica... 11 Quadro 2 Concentrações totais dos elementos químicos mais representativos em solos da
mina de São Domingos (min – max ou média ± DP)... 16 Quadro 3 Alguns exemplos de correctivos usados/testados na reabilitação de solos
contaminados... 29 2. INTER-POPULATION VARIATION ON THE ACCUMULATION AND TRANSLOCATION OF POTENTIALLY HARMFUL CHEMICAL ELEMENTS IN CISTUS LADANIFER L. FROM BRANCANES, CAVEIRA, CHANÇA, LOUSAL, NEVES CORVO AND SÃO DOMINGOS MINES IN THE PORTUGUESE IBERIAN PYRITE BELT
Table 1 Characteristics of the soils from studied mining areas (minimum – maximum;
geometric mean)... 57 Table 2 Total concentrations of chemical elements in soils from studied mining areas
(minimum – maximum; geometric mean)....…..……….………... 58 Table 3 Concentrations of chemical elements in the available fraction of the soils from the
studied mining areas (minimum – maximum; geometric mean)... 59 Table 4 Concentrations of some chemical elements (mg/kg) reported by several authors
forCistus ladanifer plants (roots and shoots) growing in mining areas and respective soils where plants were collected...
60 3. CISTUS LADANIFER PHYTOSTABILIZING SOILS CONTAMINATED WITH NON-ESSENTIAL CHEMICAL ELEMENTS
Table 1 Characterization of soils from Caveira, Lousal and São Domingos mining areas
(geometric mean (minimum – maximum)) (Santos et al., 2014a)... 80 Table 2 Total concentrations of chemical elements in soils from Caveira, Lousal and São
Domingos mining areas (mean (minimum – maximum)) ………….….…...….….….……… 82 Table 3 Concentrations of chemical elements in the available fraction of soils from Caveira,
Lousal and São Domingos mining areas (mean (minimum – maximum))... 83 Table 4 Concentrations of the chemical elements in Cistus ladanifer roots collected in Caveira,
Lousal and São Domingos mining areas (mean (minimum – maximum))... 85 Table 5 Concentrations of the chemical elements in Cistus ladanifer shoots collected in
Caveira, Lousal and São Domingos mining areas (mean (minimum – maximum))... 86 Table 6 Values of biological absorption coefficient (BAC = [total roots element]/[available soil
element]) in Cistus ladanifer collected in Caveira, Lousal and São Domingos mining areas
(minimum – maximum)... 87 Table 7 Values of translocation coefficient (TranslC = [total shoots element]/[total roots
Índice de quadros
element]) in Cistus ladanifer collected in Caveira, Lousal and São Domingos mining areas
(geometric mean (minimum – maximum))………... 88
4. MUTIELEMENTAL CONCENTRATION AND PHYSIOLOGICAL RESPONSES OF LAVANDULA PEDUNCULATA GROWING IN SOILS DEVELOPED ON DIFFERENT MINE WASTES
Table 1 Chemical characteristics of rhizosphere soils of Lavandula pedunculata growing in São Domingos mining area and non-contaminated area – Corte do Pinto (min – max; mean).
Values of the same row followed by an asterisk indicate significant differences between areas
(p < 0.05)... 106 Table 2 Total concentrations of the chemical elements in the rhizosphere soils of Lavandula
pedunculata growing in São Domingos mining area and non-contaminated area – Corte do
Pinto (min – max; mean)... 108 Table 3 Concentrations of the chemical elements in the available fraction of the rhizosphere
soils of Lavandula pedunculata growing in São Domingos mining area and non-contaminated
area – Corte do Pinto (min – max; mean)... 109 Table 4 Concentrations of the potentially hazardous elements in the roots and shoots of
Lavandula pedunculata collected in São Domingos mining area and non-contaminated area –
Corte do Pinto (min – max; mean)... 111 Table 5 Concentrations of the nutrients in the roots and shoots of Lavandula pedunculata
collected in São Domingos mining area and non-contaminated area – Corte do Pinto (min –
max; mean)... 112 Table 6 Physiological parameters in Lavandula pedunculata shoots collected in São Domingos
mining area and non-contaminated area – Corte do Pinto (min – max; mean)……….……... 115
5. COMPOSITION AND AROMATIC PROFILE OF EXTRACTS FROM CISTUS LADANIFER AND LAVANDULA PEDUNCULATA GROWING IN SÃO DOMINGOS MINING AREA
Table 1 Chemical characteristics of the soils from São Domingos mine (SD) and Corte do Pinto
(CP) areas and respective plant species collected... 132 Table 2 Chemical composition (%) of the extract, obtained in a single extraction with hexane,
from Lavandula pedunculata shoots collected in São Domingos mine (SD) and Corte do Pinto
(CP; non-contaminated area) areas (mean ± σ2; n = 3)... 135 Table 3 Concentration of some major components (mg/kg) in extracts, obtained with different
extraction solutions, from Lavandula pedunculata shoots collected in São Domingos mine (SD)
and Corte do Pinto (CP; non-contaminated area) (mean ± σ2; n = 3)... 136 Table 4 Chemical composition (%) of the extracts, obtained by sequential extraction with water
and hexane, from Lavandula pedunculata shoots collected in São Domingos mine (SD) and
Corte do Pinto (CP; non-contaminated area) (mean ± σ2; n = 3)... 137 Table 5 Chemical composition (%) of extracts, obtained with hexane, from Cistus ladanifer
shoots collected in São Domingos mine (SD) and Corte do Pinto (CP; non-contaminated area)
(mean ± σ2; n = 3)... 141 Table 6 Concentration of some major components (mg/kg) in extracts, obtained with hexane,
from Cistus ladanifer shoots collected in São Domingos mine (SD) and Corte do Pinto (CP;
non-contaminated area) (mean ± σ2; n = 3)... 142
6. POTENTIAL ENVIRONMENTAL IMPACT OF TECHNOSOLS COMPOSED OF GOSSAN AND SULFIDE-RICH WASTES FROM SÃO DOMINGOS MINE: ASSAY OF SIMULATED LEACHING
Table 1 Composition of the Technosols used for the leaching assays... 154 Table 2 Chemical characteristics of the gossan and the sulfide-rich wastes from the São
Domingos mine area and organic/inorganic wastes used as amendments (min – max or mean
value) (Santos et al. 2014a,b)... 155 Table 3 Mass (Mg) of elements leached from the sulfide-rich and gossan wastes and
respective Technosols based on the concentrations of elements in simulated leachates and
total mass of tailings in São Domingos mining area... 170 7. EFFECTS OF ORGANIC/INORGANIC AMENDMENTS ON TRACE ELEMENTS DISPERSION BY LEACHATES FROM SULFIDE-CONTAINING TAILINGS OF THE SÃO DOMINGOS MINE, PORTUGAL.
TIME EVALUATION
Table 1 Characteristics of the original sulfide mine wastes from the São Domingos mine area
and organic/inorganic wastes used as amendments (min – max)... 183 Table 2 Total concentrations of trace elements (g/kg Dry weight) in the original mine wastes
from the São Domingos mine, composed of crushed pyrite and smelting ashes, and in the
organic/inorganic wastes used as amendments (min – max)... 183 Table 3 Characteristics of mine wastes samples from different treatments, collected after one
month of incubation and at the end of the experiment (Mean ± SD; n = 4)... 185 Table 4 Multielemental composition of surface efflorescent salts from sulfide mine wastes
without (control) and with amendments application at 30 and 75 Mg/ha... 194 Table 5 Multielemental composition of minerals (μg or mg/g Dry weight) from sulfide mine
wastes without (control) and with amendments application at 30 and 75 Mg/ha, collected in two
depth (A: < 5 cm; B: ≈10 cm) after thirteen months of incubation... 202
8. CHEMICAL QUALITY OF LEACHATES AND ENZIMATIC ACTIVITIES IN TECHNOSOLS WITH GOSSAN AND SULFIDE WASTES FROM THE SÃO DOMINGOS MINE
Table 1 Chemical characteristics of the gossan and the sulfide wastes from São Domingos mine area and organic/inorganic wastes used as amendments (min – max or mean value)
(Santos et al. 2014a,b).……….………. 213
Table 2 Composition of the Technosols used in the three assays... 214 Table 3 Concentrations of anions in leachates from Technosols and gossan wastes – assay 1
(Mean ± SD; n = 3) collected at time zero (0) and after three (1º) and nine (2º) months of
incubation... 219 Table 4 Concentrations of anions in leachates of mine wastes and Technosols from assays 2
and 3 (Mean ± SD; n = 4) collected at time zero (0) and after three (1º) and nine (2º) months of incubation...
225
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9. IMPROVEMENT OF CHEMICAL AND BIOLOGICAL PROPERTIES OF GOSSAN MINE WASTES