Sorption of arsenic by composts and biochars derived from the organic fraction of municipal solid wastes: Kinetic, isotherm and oral bioaccessibility study.

The historic contamination of water and soils by arsenic (As) is an extremely alarming environmental and public health issue worldwide. This study investigated the relationship between As sorption and physicochemical properties of composts and biochars derived from the organic fraction of municipal solid wastes (OFMSW) towards the development of promising sorbents with value-added solid wastes management solutions. The sorbents were characterized and their effectiveness on the As sorption was tested. Several isothermal and kinetic sorption models were used for the prediction of sorption. Composts did not show promising sorption capacities, and in some cases, the As immobilization was practically null. In contrast, biochars achieved higher sorption performance, and the experimental data fitted well on Dubinin-Rabushkevich and Langmuir models, with higher R2 values. The maximum sorption capacities of BC700 estimated by such models were 6.495 and 170.252 mg g-1, respectively, whereas those of BC500 estimated by D-R and Langmuir models were only 0.066 and 0.070 mg g-1, respectively. In sorption kinetics, As was retained onto biochars at a faster first stage, reaching equilibrium after approximately 1 h and 2 h for initial concentrations of 10 and 100 mg L-1. The pseudo-second-order, Ritchie's second-order, Ritchie's, and Elovich models more adequately described the sorption kinetics of As onto biochars with high R2 values. Overall, the complexation and precipitation were predominant mechanisms for As sorption by OFMSW-derived biochars. Furthermore, the mathematical models indicated contributions arise from physisorption and external and internal diffusion mechanisms. Although BC700 can immobilize large As amounts, the gastric phase of the oral bioaccessibility test revealed more than 80% of the sorbed As could be released under conditions similar to a human stomach (pH~1.2). Such conclusions have given important insights about the refining of effective and eco-friendly remediation technologies for the management and rehabilitation of As-contaminated soil and water, particularly in developing countries.

Extremely acidic environment: Biogeochemical effects on algal biofilms.

The biological responses of acidobiontic species to extremely acidic waters, as those related with Acid Mine Drainage (AMD) processes, are relevant not only to understand the toxicological degree of the waters as well as the mechanisms responsible for the survival and adaptation of such organisms. Therefore, the objective of this study was to evaluate the effect of acidic pH and metals in biofilms collected in two sites a lentic permanent acid pond (AP) and a temporary acid stream (AS) affected by Acid Mine Drainage (AMD), and taking as control (C), an uncontaminated site with circumneutral pH. The results showed typical conditions of AMD-contaminated waters in sites AS and AP (pH < 3 and high concentrations of Al, Cu, Fe, Mn, Pb and Zn), which are responsible for a substantial decrease in biomass and biodiversity of biofilms (with a dominance of acidobiontic species, such as Pinnularia aljustrelica and Eunotia exigua, comparing to the control site. Also expressed by low values of photosynthetic pigments and reduced amount of proteins. In addition, such extreme acidic conditions also induced biofilms' stress, increasing antioxidant [catalase (CAT), superoxide dismutase (SOD) and biotransformation glutathione S-transferases (GSTs)] enzymes activity and also membrane damage (peroxidized lipids). However, despite the quite similar physico-chemical conditions of both AMD-contaminated sites, differences in the toxicity status between them were indirectly detected through some of the biochemical parameters [GSTs, SOD and CAT], indicating site AS has the most toxic, which fact was attributed to the higher concentrations of Pb2+ in this water. This element is recognized to be highly toxic for biota, and in such acidic conditions remains in solution, easily available to the aquatic organisms. Since pH is similar in the acid sites, the different concentrations of heavy metals in the waters might be responsible for the observed changes in the biological community at these two sites. This fact was translated in a higher capacity of this site's biofilm to cope with the negative effects of the toxicants, evidenced in a higher positive correlation with GSTs, CAT and SOD when compared to biofilms of sites AP and C.

Biogeochemical characterization of surface waters in the Aljustrel mining area (South Portugal).

Aljustrel mining area (South Portugal) is a part of the Iberian Pyrite Belt and encloses six sulfide mineral masses. This mine is classified of high environmental risk due to the large tailings' volume and acid mine drainage (AMD)-affected waters generated by sulfides' oxidation. The use of biological indicators (e.g., diatoms) revealed to be an important tool to address the degree of AMD contamination in waters. Multivariate analysis has been used as a relevant approach for the characterization of AMD processes. Cluster analysis was used to integrate the significant amount and diversity of variables (physicochemical and biological), discriminating the different types of waters, characterized by the high complexity occurring in this region. The distinction of two main marked phenomena was achieved: (1) the circumneutral-Na-Cl water type (sites DA, PF, BX, BF, RO, CB), expressing the geological contributions of the Cenozoic sediments of Sado river basin, with high diatom diversity (predominating brackish diatoms as Entomoneis alata); and (2) the acid-metal-sulfated water type (sites BM, JU, RJ, AA, MR, BE, PC, AF), reflecting both the AMD contamination and the dissolution of minerals (e.g., silicates) from the hosting rocks, potentiated by the extremely low pH. This last group of sites showed lower diatom diversity but with typical diatoms from acid- and metal-contaminated waters (e.g., Pinnularia aljustrelica). In addition to these two water types, this hierarchical classification method also allowed to distinguish individual cases in subclusters, for example, treated dams (DC, DD), with alkaline substances (lime/limestone), that changed the physicochemical dynamics of the contaminated waters.

Integrating geochemical (surface waters, stream sediments) and biological (diatoms) approaches to assess AMD environmental impact in a pyritic mining area: Aljustrel (Alentejo, Portugal).

Aljustrel mines were classified as having high environmental hazard due to their large tailings volume and high metal concentrations in waters and sediments. To assess acid mine drainage impacted systems whose environmental conditions change quickly, the use of biological indicators with short generation time such as diatoms is advantageous. This study combined geochemical and diatom data, whose results were highlighted in 3 groups: Group 1, with low pH (1.9-5.1) and high metal/metalloid (Al, As, Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn; 0.65-1032 mg/L) and SO4 (405-39124 mg/L) concentrations. An acidophilic species, Pinnularia aljustrelica, was perfectly adapted to the adverse conditions; in contrast, teratological forms of Eunotia exigua were found, showing that metal toxicity affected this species. The low availability of metals/metalloids in sediments of this group indicates that metals/metalloids of the exchangeable fractions had been solubilized, which in fact enables metal/metalloid diatom uptake and consequently the occurrence of teratologies; Group 2, with sites of near neutral pH (5.0-6.8) and intermediate metal/metalloid (0.002-6 mg/L) and SO4 (302-2179 mg/L) concentrations; this enabled the existence of typical species of uncontaminated streams (Brachysira neglectissima, Achnanthidium minutissimum); Group 3, with samples from unimpacted sites, showing low metal/metalloid (0-0.8 mg/L) and SO4 (10-315 mg/L) concentrations, high pH (7.0-8.4) and Cl contents (10-2119 mg/L) and the presence of brackish to marine species (Entomoneis paludosa). For similar conditions of acidity, differences in diversity, abundance and teratologies of diatoms can be explained by the levels of metals/metalloids.

Assessment of metal pollution in a former mining area in the NW Tunisia: spatial distribution and fraction of Cd, Pb and Zn in soil.

This study aims to evaluate the impact of the former mining Touiref district (NW Tunisia) on the spatial distribution of metal contamination. In order to characterize the metal content of the tailings and to assess how far the soils from the district could be impacted by metals, a sampling campaign was conducted. According to the spatial distribution concentration maps of potential toxic elements (PTE), the highest concentrations occur near the flotation tailings and in mining facilities and decrease abruptly with distance. These results confirm that wind is the main agent capable of dispersing metals in a W-E direction, with concentrations exceeding the standards of soil quality for Cd, Pb and Zn over several hundred metres away from the source, facilitated by the small-size fraction and low cohesion of tailings particles. Chemical fractionation showed that Pb and Cd were mainly associated with the acid-soluble fraction (carbonates) and Fe-(oxy) hydroxides, while Zn was mainly associated with Fe-(oxy) hydroxides but also with sulphides. Thus, the immobilization of metals in solution may be favoured by the alkaline conditions, promoted by carbonates dissolution. However, being carbonate important-bearing phases of Cd and Pb (but also for Zn), the dissolution facility of these minerals may enhance the release of metals, particularly far away from the mine where the physicochemical conditions can be different. Also, the metal uptake by plants in these alkaline conditions may be favoured, especially if secondary phases with high sorption ability are reduced at this site. A remediation plan to this area is needed, with particularly attention in the confinement of the tailings.

Acid Mine Drainage Effects in the Hydrobiology of Freshwater Streams from Three Mining Areas (SW Portugal): A Statistical Approach.

Aljustrel, Lousal and S. Domingos mines are located in the Iberian Pyrite Belt (IPB), one of the greatest massive sulfide ore deposits worldwide. These mines' surrounding streams are affected by Acid Mine Drainage (AMD). The main purpose of this study was to understand AMD influence in the water quality and diatom behavior. Thus, waters and diatoms were sampled in 6 sites from the 3 selected mines on winter and summer of 2016. The highest concentrations were found in acidic sites: A3 (Aljustrel-Al, Cd, Cu, Fe and Zn (and lowest pH)) and L1 (Lousal-As, Mn, Ca, Mg, SO42- and conductivity). The most abundant diatom species was Pinnularia aljustrelica with 100% of dominance in A3 and S1 acidic sites, which puts in evidence this species adaptation to AMD harsh conditions. Multivariate cluster analysis allowed us to reinforce results from previous studies, where spatial differences were more relevant than seasonal ones. In 12 years (2004-2016), and with many transformations undertaken (re-opening and rehabilitation), there is a conservative behavior in the biological species (diatoms) and physicochemical concentrations (metals, pH and sulfates) from these three mining sites. This type of biogeochemical diagnosis is necessary for the sustainable use of these waters and the prevention of the polluting process, aimed to protect the water ecosystem and its biodiversity.

Environmental Impact Assessment in the Former Mining Area of Regoufe (Arouca, Portugal): Contributions to Future Remediation Measures.

The W-Sn Regoufe mine, closed since the 1970s, was once intensively exploited for tungsten concentrates. Throughout its activity, considerable amounts of arsenopyrite-rich mine wastes were produced and, to this day, are still exposed to weathering conditions. Thus, this work aims at assessing soil contamination, using a combination of chemical, physicochemical and mineralogical analyses and sequential selective chemical extraction of the main potentially toxic elements (PTEs) in topsoils. Results show that Regoufe soils are enriched in most of the PTEs associated with the ore assemblage, but As and Cd contents far outstrip both international and national guidelines. The estimated contamination factor reveals that 67% of soil samples are classified as highly to ultra-highly contaminated. Similar distribution patterns, with the main focus around the unsealed mine adits, are observed when spatially projecting the modified degree of contamination (mCd) and arsenic contents. Fe-oxyhydroxides and organic matter demonstrate to have a preponderant role in the retention of Cd and As. In fact, despite the high PTE contents in soils, local surface waters are characterised by low metal(loid) contents and nearly neutral pH, with PTE concentrations below national thresholds for irrigation waters.

Speciation and precipitation of heavy metals in high-metal and high-acid mine waters from the Iberian Pyrite Belt (Portugal).

Acid mine waters (AMW) collected during high- and low-flow water conditions from the Lousal, Aljustrel, and São Domingos mining areas (Iberian Pyrite Belt) were physicochemically analyzed. Speciation calculation using PHREEQC code confirms the predominance of Men+ and Me-SO4 species in AMW samples. Higher concentration of sulfate species (Me-SO4) than free ion species (Men+, i.e., Al, Fe, and Pb) were found, whereas opposite behavior is verified for Mg, Cu, and Zn. A high mobility of Zn than Cu and Pb was identified. The sulfate species distribution shows that Fe3+-SO42-, SO42-, HSO4-, Al-SO4, MgSO40, and CaSO40 are the dominant species, in agreement with the simple and mixed metal sulfates and oxy-hydroxysulphates precipitated from AMW. The saturation indices (SI) of melanterite and epsomite show a positive correlation with Cu and Zn concentrations in AMW, which are frequently retained in simple metal sulfates. Lead is well correlated with jarosite and alunite (at least in very acid conditions) than with simple metal sulfates. The Pb for K substitution in jarosite occurs as increasing Pb concentration in solution. Lead mobility is also controlled by anglesite precipitation (a fairly insoluble sulfate), where a positive correlation was ascertained when the SI approaches equilibrium. The zeta potential of AMW decreased as pH increased due to colloidal particles aggregation, where water species change from SO42- to OH- species during acid to alkaline conditions, respectively. The AMW samples were supersaturated in schwertmannite and goethite, confirmed by the Men+-SO4, Men+-Fe-O-OH, or Men+-S-O-Fe-O complexes identified by attenuated total reflectance infrared spectroscopy (ATR-IR). The ATR-IR spectrum of an AMW sample with pH 3.5 (sample L1) shows well-defined vibration plans attributed to SO4 tetrahedron bonded with Fe-(oxy)hydroxides and the Men+ sorbed by either SO4 or Fe-(oxy)hydroxides. For samples with lower pH values (pH ~ 2.5-samples SD1 and SD4), the vibration plans attributed to Men+ sorption are not evidenced, indicating its release in solution. The sorption of heavy metals on the first precipitated simple metal sulfates was ascertained by scanning electron microscopy coupled with X-ray spectrometry (SEM-EDX), where X-ray maps of Cu and Zn confirm a distribution of both metals in the melanterite structure.

Copper, zinc and lead biogeochemistry in aquatic and land plants from the Iberian Pyrite Belt (Portugal) and north of Morocco mining areas.

The ability of aquatic (Juncus effusus L., Scirpus holoschoenus L., Thypha latifolia L. and Juncus sp.) and land (Cistus ladanifer L., Erica andevalensis C.-R., Nerium oleander L., Isatis tinctoria L., Rosmarinus officinalis L., Cynodon dactylon L. and Hordeum murinum L.) plants from Portugal (Aljustrel, Lousal and São Domingos) and Morocco (Tighza and Zeida) mining areas to uptake, translocate and tolerate heavy metals (Cu, Zn and Pb) was evaluated. The soils (rhizosphere) of the first mining area are characterized by high acidity conditions (pH 2-5), whereas from the second area, by alkaline conditions (pH 7.0-8.5). Physicochemical parameters and mineralogy of the rhizosphere were determined from both areas. Chemical analysis of plants and the rhizosphere was carried out by inductively coupled plasma emission spectrometry. The sequential chemical extraction procedure was applied for rhizosphere samples collected from both mining areas. In the acid conditions, the aquatic plants show a high capacity for Zn bioaccumulation and translocation and less for Pb, reflecting the following metal mobility sequence: Zn > Cu > Pb. Kaolinite detected in the roots by infrared spectroscopy (IR) contributed to metal fixation (i.e. Cu), reducing its translocation to the aerial parts. Lead identified in the roots of land plants (e.g. E. andevalensis) was probably adsorbed by C-H functional groups identified by IR, being easily translocated to the aerial parts. It was found that aquatic plants are more efficient for phytostabilization than bioaccumulation. Lead is more bioavailable in the rhizosphere from Morocco mining areas due to scarcity of minerals with high adsorption ability, being absorbed and translocated by both aquatic and land plants.

Comparison of adipocere formation in four soil types of the Porto (Portugal) district.

Four typical soils of the Porto (Portugal) area were characterized and used to study the decomposition of buried pieces of pork meat under controlled laboratory experiments (an 8 month experiment with a relatively high soil moisture and a 1 month experiment with relatively low soil moisture). The soils types were: organic, sandy, gravel and clay-gravel soils. Soils were characterized for their grain size distribution, pH, water content, organic matter percentage and mineral composition. Four free fatty acids (myristic, palmitic, oleic and stearic) were analysed (using a methodology based on an extraction step followed by a derivatization reaction and high performance liquid chromatography analysis) in soil samples as a sign of adipocere formation. The direct sensorial analysis of the buried sample residues and the free fatty acids profiles of the sampled soils showed that sandy and clay-gravel soils (in a low moisture environment) slowed the normal decomposition process promoting the formation of adipocere. Nevertheless, this apparent soil effect is indirect and a consequence of the different water retention and permeability of the soils. Thus, the water content of the soils is a crucial factor for adipocere formation.