Interaction of the water soluble fraction of MSW-composts with Pb(II) and Cu(II) ions.

In this study we report on the interactions between the water-soluble fraction (WSF) of two municipal solid waste composts (C1- and C2-WSF) with Pb(II) and Cu(II) ions at pH 4.5. The Me(II) addition to the compost-WSFs led to the formation of soluble Me(II)-organic complexes (as highlighted by FT-IR spectroscopy), and to a decrease of the trace metals' solubility, which was greater for Pb(II) than Cu(II). This was due to the formation of insoluble Me(II) complexes involving the water-soluble organic carbon (WSOC) and the inorganic anions within both WSFs [1.10 and 0.62 mmol L-1 and 2.06 and 0.42 mmol L-1 of Pb(II) and Cu(II) precipitated from C1- and C2-WSF respectively, when 6.4 mmol L-1 Me(II) was added]. A loss of WSOC from both WSFs, i.e. ∼13% and <5%, was detected in the systems containing 6.4 mmol L-1 Pb(II) and Cu(II) respectively. A significant contribution in the formation of Pb(II) precipitates was also due to phosphate, chloride and sulphate anions, since their concentrations in the WSF decreased of 80, 25 and 90%, respectively, after the addition of 6.4 mmol L-1 Pb(II). A decrease of phosphate anions in both WSFs (∼30%) was found in the systems containing Cu(II).

In Situ Fixation of Metal(loid)s in Contaminated Soils: A Comparison of Conventional, Opportunistic, and Engineered Soil Amendments.

This study aimed to assess and compare the in vitro and in vivo bioaccessibility/bioavailability of As and Pb in a mining contaminated soil (As, 2267 mg kg(-1); Pb, 1126 mg kg(-1)), after the addition of conventional (phosphoric acid), opportunistic [water treatment residues (WTRs)], and engineered [nano- and microscale zero valent iron (ZVI)] amendments. Phosphoric acid was the only amendment that could significantly decrease Pb bioaccessibility with respect to untreated soil (41 and 47% in the gastric phase and 2.1 and 8.1% in the intestinal phases, respectively), giving treatment effect ratios (TERs, the bioaccessibility in the amended soil divided by the bioaccessibility in the untreated soil) of 0.25 and 0.87 in the gastric and intestinal phase, respectively. The in vivo bioavailability of Pb decreased in the phosphate treatment relative to the untreated soil (6 and 24%, respectively), and also in the Fe WTR 2% (12%) and nZVI-2 (13%) treatments. The ZVI amendments caused a decrease in As bioaccessibility, with the greatest decrease in the nZVI2-treated soil (TERs of 0.59 and 0.64 in the gastric and intestinal phases, respectively). Arsenic X-ray absorption near-edge spectroscopy analysis indicated that most of the As in the untreated soil was present as As(V) associated with Fe mineral phases, whereas in the treated soil, the proportion of arsenosiderite increased. Arsenite was present only as a minor species (3-5%) in the treated soils, with the exception of an nZVI treatment [∼14% of As(III)], suggesting a partial reduction of As(V) to As(III) caused by nZVI oxidation.

Stabilising metal(loid)s in soil with iron and aluminium-based products: microbial, biochemical and plant growth impact.

Four iron and aluminium-based products, including red mud (RM), hematite (Fe2O3), an iron-rich water treatment residual (Fe-WTR) and amorphous Al hydroxide (Al-OH), were evaluated for their effectiveness at stabilising As and heavy metals (i.e. Cd, Cu, Pb, Zn) in a circumneutral contaminated soil [As (2105 mg kg(-1)), Cd (18 mg kg(-1)), Cu (264 mg kg(-1)), Pb (710 mg kg(-1)), Zn (522 mg kg(-1))]. Treatment impacts on soil microbial and biochemical features (i.e. microbial biomass-C, microbial counts, 16S rRNA PCR-TTGE of culturable bacteria, dehydrogenase, urease and ß-glucosidase activity, Biolog derived parameters-AWCD and richness) as well as bean (Phaseolus vulgaris) and wheat (Triticum vulgare) growth were also assessed. After 6 months equilibration, all the amendments (application rate 3% w/w) but RM reduced labile As while only Al-OH reduced the concentration of water-soluble heavy metals. Despite the highest bioavailability of contaminants, most of the soil microbial and biochemical features monitored (i.e. microbial biomass-C, total bacterial counts, dehydrogenase activity and AWCD) were significantly higher in the RM-soil. Bean germination was completely inhibited in RM-soil while wheat growth was similar to that of the control. The Al-OH treatment was best overall, promoting microbial abundance, diversity and activity while increasing bean and wheat growth and reducing As accumulated in plant shoots. Results suggest that Al-OH is a suitable candidate for field evaluations while the use of RM in the remediation of circumneutral or subalkaline contaminated soils should be reconsidered.

Arsenic mobilization by citrate and malate from a red mud-treated contaminated soil.

The mobility and bioavailability of As in the soil-plant system can be affected by a number of organic acids that originate from the activity of plants and microorganisms. In this study we evaluated the ability of citrate and malate anions to mobilize As in a polluted subacidic soil (UP soil) treated with red mud (RM soil). Both anions promoted the mobilization of As from UP and RM soils, with citrate being more effective than malate. The RM treatment induced a greater mobility of As. The amounts of As released in RM and UP soils treated with 3.0 mmol L citric acid solution were 2.78 and 1.83 µmol g respectively, whereas an amount equal to 1.73 and 1.06 µmol g was found after the treatment with a 3.0 mmol L malic acid solution. The release of As in both soils increased with increasing concentration of organic acids, and the co-release of Al and Fe in solution also increased. The sequential extraction showed that Fe/Al (oxi)hydroxides in RM were the main phases involved in As binding in RM soil. Two possible mechanisms could be responsible for As solubilization: (i) competition of the organic anions for As adsorption sites and (ii) partial dissolution of the adsorbents (e.g., dissolution of iron and aluminum oxi-hydroxides) induced by citrate or malate and formation of complexes between dissolved Fe and Al and organic anions. This is the first report on the effect of malate and citrate on the As mobility in a polluted soil treated with RM.

Assessment of the use potential of edible sea urchins (Paracentrotus lividus) processing waste within the agricultural system: influence on soil chemical and biological properties and bean (Phaseolus vulgaris) and wheat (Triticum vulgare) growth in an amended acidic soil.

In this study we evaluated the influence of ground purple sea urchin (Paracentrotus lividus) endoskeletons, a processing waste common to all edible sea urchin plants, on the chemical, biochemical and microbiological features of an acidic (pH 5.65) sandy-loam soil. The purple sea urchin endoskeletons were characterized by a high content of total carbonates (∼94%), a moderately alkaline pH in water (pH 7.88) and electrical conductivity values (3.55 mS/cm) very similar to those of commercial lime. To evaluate the influence of the P. lividus endoskeletons on soil properties four different amendment rates were tested, notably 0.5, 1.0, 3.0 and 5.0% based on soil dry weight, and the effects compared with those recorded on unamended control soil. The addition of the purple sea urchin processing waste caused an immediate and significant pH increase which was positively related to the rate of the amendment addition. After a six months equilibration period, the differences in soil pH were still evident and significant increases of electrical conductivity and available phosphorus were also detected in soils with the higher amendment rates. The number of heterotrophic and cellulolytic bacteria and actinomycetes significantly increased after amendment addition while the number of culturable fungi steadily declined. The analysis of the Biolog Community Level Physiological Profile indicated a clear influence of the purple sea urchin processing waste on the structure of the native microbial community while a significant increase of microbial functionality (i.e. dehydrogenase activity) was recorded in soil treated with the higher amendment rates (i.e. 3.0 and 5.0%). The improvement of microbial abundance and functionality as well as the change of the microbial community structure were ascribed to the pH shift induced by the P. lividus processing waste. To investigate possible effects on soil fertility, dwarf bean (Phaseolus vulgaris) and wheat (Triticum vulgare) growth were also assessed in a pot experiment. Plant growth was unaffected (wheat) or stimulated (bean) by the amendment addition in the 0.5-3.0% range while the higher amendment rate (i.e. 5.0%) was detrimental for both plant species indicating a phytotoxic effect which could be due to different factors such as an excess of calcium in soil, a suppression of Mg uptake or the higher EC values detected at the highest amendment rate. It is concluded that ground P. lividus endoskeletons have potential as a soil amendment to ameliorate chemical and biological properties of acidic Mediterranean soils. This seems particularly relevant, especially at the lower amendment rates, since for the first time, a sustainable management system is proposed for P. lividus processing waste, which foresees economic value in the sea urchin by-product through its re-use within the agricultural production system.

Oxidation of caffeic acid by Fe(III) trapped in a Ca-polygalacturonate network.

With the aim to verify if Fe(III) ions accumulated in a network of Ca-polygalacturonate (PGA) may promote the oxidation of caffeic acid (CAF) the interaction at pH 5.0 between CAF and Fe(III) ions trapped in a PGA was studied. The sorption kinetics evidenced a great affinity of CAF towards the Fe-PGA matrix. Chromatographic tests showed that the interaction leads to the formation of products which can be considered as CAF oligomers characterized by FT-IR spectra similar to those of natural humic acids. Tests carried out under nitrogen suggest that at pH 5.0 oxygen does not affect the nature of these oxidation products. Oxygen was hypothesized to exert a direct action on the redox process by oxidizing the Fe(II) ions, produced by oxidation of CAF, to Fe(III) thus regenerating oxidizing sites. A possible mechanism of formation of the polymers was proposed that implies that the CAF oxidation leads to highly reactive species such as semiquinones which give rise, by an oxidative coupling reaction, to the formation of oligomers that can aggregate through secondary bonds to produce more complex structures as those that characterize humic acids.

Municipal solid waste compost as a novel sorbent for antimony(V): adsorption and release trials at acidic pH.

The ability of two municipal solid waste composts (MSW-Cs) to sorb antimony(V) in acidic conditions (pH 4.5) was investigated. Sorption isotherms and kinetics showed that both MSW-Cs could sorb antimony(V), even if in different amounts (~ 0.18 and 0.24 mmol g-1 of Sb(V) by MSW-C1 and MSW-C2, respectively). These differences were ascribed to the chemical composition of composts, as well as to the total acidity of their humic substances. The Sb(V) sorption by both MSW-Cs followed a pseudo-second-order kinetic model, while the sorption isotherms data fitted the Freundlich model better than the Langmuir one. The humic acids extracted from composts contributed to 4.26 and 8.24% of Sb(V) sorption by MSW-C1 and MSW-C2 respectively. SEM-EDX spectra of the MSW-C+Sb(V) systems showed a certain association of Ca(II) with Sb(V), while sequential extraction procedures indicated that more than 80% of the Sb(V) sorbed was strongly retained by MSW-Cs. On the other hand, treatment with oxalic acid at pH 4.5 favored the release of more than 98 and 65% of the Sb(V) sorbed by MSW-C1 and MSW-C2 respectively, supporting a possible role of calcium in Sb(V) retention. The results from this study suggest that MSW-Cs could be used as amendments for the in-situ immobilization of Sb(V) in acidic-polluted soils.

Possible role of the polyuronic components in accumulation and mobilization of iron and phosphate at the soil--root interface.

With the aim to investigate the role of the polyuronic components in the accumulation of iron and phosphate at the soil-root interface, the interactions of Ca-polygalacturonates (PGAs) with Fe(III) and P ions and of Fe(III)-Ca-polygalacturonates (Fe-PGAs) with P ions were studied at pH 4.7. The role of citric, malic and pyruvic acids in the mobilization of Fe(III) and P, in the presence and absence of Ca(II) 2.5mM, was also investigated. The sorption kinetics evidenced that P diffuses freely through the calcium polysaccharidic matrix whereas Fe(III) accumulates as an hydroxypolymer. The sorption kinetics of P by the Fe-PGA indicated that the amount of P sorbed increases with increasing its initial concentration up to a constant value equal to 0.98micromol/3.87micromolmg(-1) of Fe(III)-polymer trapped. The FT-IR spectra of the P-Fe-PGA systems, show bands attributable to P-O(H) stretching vibrations. The study of systems with a constant initial P amount and varying Fe(III) amounts allowed to hypothesize that phosphate settles down inside holes formed by the carboxylate groups of galacturonic units. Citric and malic acids showed to be active in the mobilization of both Fe and P whereas pyruvic acid appeared inactive.

Reduction of Cr(VI) by caffeic acid.

In the soil-plant system, the Cr(VI) toxicity can be moderated through redox reactions involving phenolic substances. In such a context, we report the reducing activity of caffeic acid (CAF) towards Cr(VI) in aqueous phase. The redox reaction between Cr(VI) and CAF was studied as a function of both time and pH at different initial metal concentrations. The reaction was particularly effective at pH 2.5. The kinetic data indicate that the reaction proceeds through two steps: the first is faster and involves four electrons, the latter, which is slower, five electrons. The chromatograms evidence the formation of oxidation products (OP) with a different redox activity towards Cr(VI). A yield of Cr(III) equal to that obtained at pH 2.5 and pH 3.1 in about 7 and 25 h, respectively, was reached at pH 4.2 only after a much longer reaction time (50h). At pH>4.2 the reaction occurred even more slowly, and its kinetic trend was more and more difficult to study at pH values higher than 5.0 due to the formation of precipitates. Other phenolics investigated (o-, m-, p-coumaric acids) showed a reducing activity negligible compared to that of CAF: about 30% of p-coumaric acid was oxidized at pH 2.5 only after two months of reaction.

Influence of lead in the sorption of arsenate by municipal solid waste composts: metal(loid) retention, desorption and phytotoxicity.

The ability of two municipal solid waste composts (MSW-C) to sorb As(V) in the presence of Pb(II) and in acidic conditions was investigated. Sorption isotherms and kinetics showed that both MSW-C were able to sorb As(V) in a similar way (∼0.24mmolg-1 MSW-C), but only when Pb(II) was present (0.45mmolL-1). The concomitant sorption of Pb(II) by both MSW-C (∼0.40mmolg-1) suggested that the metal cation was likely acting as bridging element between the negatively charged functional groups of composts and As(V). SEM-EDX analysis of the MSW-C+Pb(II)+As(V) systems supported the association between Pb(II) and As(V), while sequential extraction procedures and organic acids treatment showed that As(V) was strongly retained by MSW-C+Pb(II) and suggested the presence of different interaction types between As(V) and Pb(II). Plant growth experiments highlighted the key role of Pb(II) in the reduction of As(V)-phytotoxicity for triticale plants (×Triticosecale Wittm.) in the presence of MSW-C.

Copper(II) and lead(II) removal from aqueous solution by water treatment residues.

In this study, we investigated the ability of Fe- and Al-based water treatment residues (Fe- and Al-WTR) to accumulate Pb(II) and Cu(II) at pH 4.5. The role of the inorganic and organic fractions of WTRs in metals sorption was also assessed. Sorption isotherms showed a higher sorption of Pb(II) by both WTRs with respect to Cu(II) (e.g. 0.105 and 0.089 mmol g(-1) of Pb(II) and Cu(II) respectively sorbed by Fe-WTR). Fe-WTR revealed a stronger sorbent for both metals than Al-WTR. The amount of Pb(II) and Cu(II) sorbed by Fe-WTR was about the 69% and 63% higher than that sorbed by the Al-WTR. The organic matter of Fe- and Al-WTR contributed to about 26% and 8.5% respectively in the sorption of both metals. The sequential extraction procedure showed that the greatest amount of metals sorbed by both WTRs were tightly bound and not extractable, and this was particularly apparent for Cu(II). The FT-IR spectra indicated the formation of inner-sphere complexes between the Fe(Al)-O nucleus and Pb(II) and Cu(II). Moreover, the FT-IR spectra also suggested that the humic fraction of WTRs interacted, through the carboxylate groups, with Cu(II) and Pb(II) by forming mainly monodentate and bidentate complexes, respectively.

Detoxification Processes from Vanadate at the Root Apoplasm Activated by Caffeic and Polygalacturonic Acids.

In the root apoplasm, V(V) and V(IV) toxicity can be alleviated through redox and complexation reactions involving phenolic substances and the polyuronic components. In such context we report the role of polygalacturonic acid (PGA) on the reducing activity of caffeic acid (CAF) towards V(V). The redox reaction was particularly effective at pH 2.8 leading to the formation of oxidation products with redox activity towards V(V). An o-quinone was identified as the first product of the reaction which is further involved in the formation of CAF dimers. At pH ≥ 3.6 the redox activity decreased and a yield in V(IV) equal to 38, 31, 21 and 14% was found at pH 3.6, 4.0. 5.0 and 6.0 respectively compared with that obtained at pH 2.8. The redox reaction was faster in the presence of PGA and a higher yield of V(IV) was found in the 4.0-6.0 pH range with respect to the CAF-V(V) binary system. The higher efficiency of the redox reaction in the presence of PGA was related with the ability of PGA to bind V(IV). The biological significance of the redox reaction between CAF and V(V), as well as the role of PGA in such reaction, was established "in vivo" using triticale plants. Results showed that PGA reduced significantly the phytotoxic effects of the V(V)-CAF system.

Water treatment residues as accumulators of oxoanions in soil. Sorption of arsenate and phosphate anions from an aqueous solution.

Here we report a survey addressed to determine, at different pH values (pH 4.0, 7.0 and 9.0), the ability of two different water treatment residues, a Fe-based (Fe-WTR) and an Al-based (Al-WTR), to accumulate arsenate and phosphate anions from an aqueous solution and to define the mechanism which regulate the sorption of these anions. Fe-WTR showed a greater As(V) and P(V) sorption capacity respect to Al-WTR at all the pH values investigated, in particular at pH 4.0. The greater capacity of the Fe-WTR to accumulate phosphate at pH 4.0 seems to be linked to the higher content of manganese ions compared to Al-WTR, which can give rise, with phosphate ions, to the formation of MnHPO4 precipitates. Sequential extraction of As(V)- or P(V)-WTRs suggested that the main mechanism governing the sorption of both two anions likely involve the formation of inner-sphere surface complexes [Fe/Al-O-As(P)]. Such a coordination mode was supported by the FT-IR spectra that exhibit well resolved band at 865cm(-1) and 1040cm(-1) attributable to ν(As-O) or ν(P-O) stretching vibration, respectively.

Formation of biopolymers owing to the oxidation of esculetine by Cu(II) ions in a Ca-polygalacturonate network.

Pectic acids participate in the transport of heavy metal ions in the root apoplasm by establishing interactions that can lead to their partial or total immobilization. The ions accumulated can be mobilized by phenolic compounds and organic acids of the root exudates. In this context, we tested, in aqueous phase, the ability of malic acid and esculetine (ESC) to mobilize the Cu(II) ions accumulated in a Ca-polygalacturonate matrix (Ca-PGA) used as a model of the root apoplasm. The results show that at pH 5.0 and 6.0 malic acid mobilizes about 22% and 34% of the Cu(II) accumulated, respectively, whereas ESC about 12% and 25%. ESC was found to cause the reduction of Cu(II) to Cu(I) with formation of ESC oxidation products. The study of the Cu(II)-ESC binary system evidenced that one molecule of ESC reduces one Cu(II) ion with formation of semiquinonic radicals that couple to form two dimers. The Cu(II) reduction by ESC was found faster in the presence of malic acid.

Long-term influence of red mud on As mobility and soil physico-chemical and microbial parameters in a polluted sub-acidic soil.

In this study we evaluated the efficiency of red muds (RM, a bauxite residue) to immobilize the arsenic present in a polluted sub-acidic soil (UP-soil; total As 2428 mg kg(-1)) and to influence some chemical, biochemical and microbiological properties after 2 years since RM addition. The RM addition caused a pH increase, a striking decrease of total organic carbon and a significant increase of water-soluble C, N and P. The analysis of As mobility through sequential extraction showed a reduction of the water-soluble arsenic in the RM-soil compared to the UP-soil (3.44% and 5.59% of the total As respectively) and a remarkable increase of the residual (non extractable) arsenic fraction in the RM-soil (>300% compared to UP-soil). RM addition increased significantly the microbial abundance and the activity of selected enzymes (dehydrogenase, urease) with respect to UP-soil while had a major influence on the structure of soil microbial communities as evaluated by the Biolog Community Level Physiological Profile. The reduced As mobility, together with an increase of C, N and P labile-pool (likely originating from a "de-structuring effect" of RM on the soil organic matter) were identified as the key factors affecting the biological activity in the RM-treated soil.

Role of the Ca-pectates on the accumulation of heavy metals in the root apoplasm.

In order to better understand the processes that regulate the accumulation in the apoplasm of heavy metals and their mobilization by the plant metabolites it is essential to study the mechanisms that regulate the interactions between metal ions and pectins. In such a context, the sorption of Cd(II), Zn(II), Cu(II) and Pb(II) from single and multi-metal solutions, by a Ca-polygalacturonate gel with a degree of esterification of 18.0 (PGAM(1)) and 65.5% (PGAM(2)) was studied in the 3.0-6.0 pH range in the presence of CaCl(2) 2.5mM. The sorption of Cr(III) from single metal solution was also considered. The results show that the amount of each metal ion sorbed increases with increasing the initial metal ion concentration and pH. The data from the single metal solution tests show that at pH 6.0 the affinity of the metal ions towards the PGAM(1) matrix follows the order: Cr(III)>Cu(II)≅Pb(II)≫Zn(II)≅Cd(II). The simultaneous sorption of the bivalent metal ions by the PGAM(1) gels indicates that Pb(II) is selectively sorbed. The FT-IR spectra show that the carboxylate groups are mainly responsible for the metal ion coordination. The ability of PGAM(2) to accumulate Cr(III), Cu(II), and Pb(II) was lower than that found in the PGAM(1) systems whereas the sorption of Zn(II) and Cd(II) was negligible.

Influence of the pH on the accumulation of phosphate by red mud (a bauxite ore processing waste).

In the present work we investigated the interactions established between red mud (RM) and phosphate anions (P) at pH 4.0, 7.0 and 10.0. The amount of P sorbed by RM (P-RM) increased as the pH decreased being equal to 4.871 mmol g(-1) at pH 4.0, 0.924 mmol g(-1) at pH 7.0, and 0.266 mmol g(-1) at pH 10.0. Sequential extractions' data of P-RM equilibrated at pH 4.0 and 7.0, suggested that the phosphate sorption at these pH values was mainly regulated by two different mechanisms that gave rise to a chemical adsorption on RM phases, and to the formation of metal phosphate precipitates. By contrast, at pH 10.0 the P-sorption was regulated by a chemisorption mechanism on Fe-Al phases of RM. These findings were supported by FT-IR analysis, which showed a broad band at 1114 and 1105 cm(-1) in P-RM spectra at pH 4.0 and 7.0 respectively, attributable to P-O(H) stretching nu(3)-modes associated to inner-sphere complexes of phosphate on Fe-Al phases, or alternatively to stretching vibrations of PO(4)(3-) tetrahedra, arising from a precipitate of aluminium phosphate. Importantly, the FT-IR spectroscopy showed a phosphate-promoted dissolution of tectosilicates, notably cancrinite and sodalite, in RM exchanged with phosphate at pH 4.0 and 7.0.

Accumulation and mobilization of arsenate by Fe(III) polyions trapped in a Ca-polygalacturonate network.

The role of Fe(III) stored at the soil-root interface in the accumulation of arsenate and the influence of citric acid on the As(V) mobility were investigated by using Ca-polygalacturonate networks (PGA). The results indicate that in the 2.5-6.2 pH range Fe(III) interacts with As(V) leading to the sorption of As(V) on Fe(III) precipitates or Fe-As coprecipitates. The FT-IR analysis of these precipitates evidenced that the interaction produces Fe(III)-As(V) inner-sphere complexes with either monodentate or bidentate binuclear attachment of As(V) depending on pH. In the 3.0-6.0 pH range, As(V) diffuses freely through the polysaccharidic matrix that was found to exert a negligible reducing action towards As(V). At pH 6.0 citric acid is able to mobilize arsenate from the As-Fe-PGA network through the complexation of the Fe(III) polyions that leads to the release of As(V).