Cadmium and arsenic adsorption in aqueous systems in the presence of monosilicic acid

The effect of different concentrations of monosilicic acid on the sorption capacity of quartz sand, diatomite, zeolite, and brown coal with respect to cadmium and arsenic has been studied in laboratory conditions. The applicability of different adsorption models, including exponential, semilogarithmic, and linear dependences, as well as the Langmuir and Freundlich equations, has been compared. An increase in monosilicic acid concentration from 0 to 2 mM increased the sorption capacity of all materials. It has been suggested that either the interaction of monosilicic acid with a pollutant takes place directly in the solution followed by sorption of the reaction products on the surface or in the pores of the sorbent, or first adsorption of the monosilicic acid by the sorbent occurs followed by interaction of the sorbed silicic acid with cadmium and arsenic; it is also possible that both process proceed in parallel.     

Characterization of kaolinite in the hardsetting clay fraction using atomic force microscopy,X-ray diffraction,and the Rietveld method

Purpose

Brazilian soils that present extremely hard sub-superficial horizons when dry and friable when humid are similar to the Australian and South African hardsetting horizons whose hardness can be mainly related to low crystallinity. Studies involving refinement by the Rietveld method with X-ray diffraction (RM-XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), and their relation have not been carried out in hardsetting horizon soils. Thus, the objective of this study is to obtain information about the kaolinite in the hardsetting horizon of a Yellow Argisol clay fraction, taking into consideration the results of isomorphic substitution, crystallite average size, and microstrains, relating them to particle image analysis regarding their morphology and size.

Materials and methods

Soil samples were collected in the hardsetting horizon of a Yellow Argisol in the Coastal Tablelands region, which covers the whole Brazilian Northeast coast and part of the Southeast region. The sample was powdered, sieved, and submitted to dispersion and physical fractioning process by sedimentation. The clay fraction was analyzed by RM-XRD, AFM, and SEM techniques.

Results and discussion

The RM-XRD provided improvement of indices with isomorphic substitutions in the goethite [Fe_0.70Al_0.30O(OH)], kaolinite [Al_1.44Fe_0.56Si₂O₅(OH)₄], and halloysite [Al_1.42Fe_0.58Si₂O₅(OH)₄]; 29 nm crystallite average size; 5 × 10^?3 microstrain; and 49.5% kaolinite. AFM analyses indicated particle average size from 80 to 250 nm and average height from 60 to 80 nm. By relating this data, it was possible to estimate that the particles under analysis are kaolinite composed of 3 to 9 crystallites and stacking of 88 to 112 layers.

Conclusions

The process, analyses, and comparisons such as crystallographic and morphologic information about the kaolinite mineral particles contribute to the comprehension of the hardsetting horizon soil nature as well as other soils that present minerals with a high degree of isomorphic substitution.

     

Protective effects of extra virgin olive oil phenolics on oxidative stability in the presence or absence of copper ions

The antioxidant activity of the phenolic fraction of extra virgin olive oil was assessed in samples that had a decreasing content of antioxidants in the presence and absence of copper ions as a catalyst of autoxidation. The oxidation process was evaluated by measuring primary and secondary oxidation products. Changes in phenols and tocopherols were investigated by high-performance liquid chromatography. Both the total phenol content and their antioxidant activity were monitored by spectrophotometric assays (with Folin-Ciocalteu and ABTS*+ reagents). The important role of phenolic compounds (particularly the o-diphenols) in protection from autoxidation was confirmed. However, the tocopherols were more quickly consumed in oils that had the lowest content of o-diphenols, which also showed evidence of an ability to chelate copper. In particular, a dramatic decrease was observed in the isomeric form of decarboxymethyl-oleuropein aglycone after addition of the metal, despite its significant increase in samples stored in the absence of copper.     

Study of the reactions between (+)-catechin and furfural derivatives in the presence or absence of anthocyanins and their implication in food color change

(+)-catechin was separately incubated with furfural or with 5-(hydroxymethyl)furfural, and the formation of new oligomeric bridged compounds having flavanol units linked by furfuryl or 5-hydroxymethylfurfuryl groups was observed. LC/ESI-MS analyses detected four dimeric adducts along with intermediate adducts in each solution, and reaction was faster with furfural than with hydroxymethylfurfural. In addition, new compounds exhibiting the same UV--visible spectra as xanthylium salts with absorption maxima around 440 nm were also detected. When malvidin 3-O-glucoside or cyanidin 3-O-glucoside was added to the mixtures, new oligomeric colorless and colored pigments involving both (+)-catechin and anthocyanin moieties were detected, showing thus that the two polyphenols competed in the condensation process. Among the obtained colored pigment adducts, two dimeric compounds in which the flavanol was bridged to the anthocyanin were observed. Their UV-visible spectra were similar to the spectrum of malvidin 3-O-glucoside, but their maximum in the visible region was bathochromically shifted.     

Structural changes in natural actomyosin and surimi from ling cod (Ophiodon elongatus) during frozen storage in the absence or presence of cryoprotectants

Surimi and natural actomyosin (NAM) from ling cod (Ophiodon elongatus) were subjected to frozen storage in the absence or presence of cryoprotectants (sorbitol, sucrose, lactitol, and Litesse, either individually or in combination). Effects of frozen storage were studied for NAM frozen at -10 degrees C for 10 days and for surimi after eight freeze-thaw cycles. A commercial blend cryoprotectant (4% sucrose and 4% sorbitol), individual cryoprotectants at 8%, and optimal blends at 4, 5.5, 6, and 8%, were effective in maintaining the gel strength of surimi and NAM gels. Surimi or NAM frozen in the absence of cryoprotectants or with only 4% individual cryoprotectants, showed increased percent alpha-helical content by Raman analysis. Increased disulfide content was also observed in the treatment without cryoprotectants by the Raman SS stretching band and by chemical determination. Tyrosine residues were in a buried environment before and after freezing for all treatments, and surface hydrophobicity measured by 1-anilinonaphthalene-8-sulfonate decreased after frozen storage in the absence of cryoprotectants.     

Investigation of the antioxidant behavior of air- and freeze-dried aromatic plant materials in relation to their phenolic content and vegetative cycle

The total phenolic and flavonoid content of the aerial parts of five aromatic plants harvested at different periods was estimated, and their antioxidant capacity was evaluated. Major phenolic compounds present in their extracts were determined by RP-HPLC. The results demonstrated different amounts of total phenolic compounds and various degrees of antioxidant activity depending on the plant species, the time of harvest, and the drying method employed. Extracts from air-dried Mentha viridis L., Origanum majorana L., and Rosmarinus officinalis L. demonstrated the greatest efficacy during the flowering stage, in which the identified flavonoids were found in significantly higher amounts, whereas phenolic acids were found in their lowest concentration. Extracts from air-dried Laurus nobilis L. and Foeniculum vulgare Mill were less efficient in terms of antioxidant activity, with the highest values being observed during the early fruiting stage. This stage was characterized by the lowest flavonoid content and high phenolic acid content, except for L. nobilis L. extracts. Overall, the amount of identified phenolic acids did not vary considerably within the investigated year. The total phenolic concentration in all plant extracts decreased significantly when freeze-dried rather than air-dried samples were used. The HPLC analysis further supported the above for most of the phenolic compounds present in the extracts, except for hydroxybenzoic acids, which were better retained during the freeze-drying process.     

Dynamics of upward and downward N2O and CO2 fluxes in ploughed or no-tilled soils in relation to water-filled pore space, compaction and crop presence

Sharp peaks in nitrous oxide (N₂O) fluxes under no-tillage in wet conditions appear to be related to near surface soil and crop cover conditions. Here we explored some of the factors influencing tillage effects on short-term variations in gas flux so that we could learn about the mechanisms involved. Field investigations revealed that a cumulative emission of 13 kg N₂O–N ha⁻¹ over a 12-week period was possible under no-tillage for spring barley. We investigated how reducing crop cover and changing the structural arrangement of the water-filled pore space (WFPS) by short-term laboratory compaction influenced N₂O and carbon dioxide (CO₂) fluxes in upward and downward directions in core samples from tilled and untilled soil. Increasing the downward flux of N₂O within a soil profile by changing soil or moisture conditions may increase the likelihood of its further reduction to N₂ or dissolution. We took undisturbed cores from 3 to 8 cm depth, equilibrated them to −1 or −6 kPa matric potential, incubated them and measured N₂O and CO₂ fluxes from the upper and lower surfaces in a purpose-designed apparatus before and after compaction in an uniaxial tester. We also measured WFPS, air permeability, bulk density and air-filled porosity before and after compaction. Spring barley was tested in 1999 and winter barley in 2000.Fluxes of N₂O were from 1.5 to 35 times higher from no-tilled than ploughed even where the soil was of similar bulk density. Reduction of the crop cover increased CO₂ flux and could reduce N₂O flux. The effects of structural changes induced by laboratory compaction on the fluxes of N₂O and CO₂ were not influenced greatly by the tillage and crop cover treatments. Fluxes from the upper surfaces of cores (corresponding to 3 cm soil depth, upwards direction) could be up to 100 times greater (N₂O) or 8 times (CO₂) than from the lower surfaces (8 cm depth, downwards direction). These differences between surfaces were greatest when N₂O fluxes were very high in no-tilled soil (4.2 mg N₂O–N m⁻² h⁻¹) as occurred when WFPS exceeded 80% or became blocked with water, an effect that was increased by our compaction treatment. In general N₂O fluxes increased with WFPS. The production and emission of N₂O were strongly influenced by the soil physical environment, the magnitude of the water-filled pore space and continuity of the air-filled pore space in particular, produced in no-till versus plough cultivation.     

Microbial biomass,N mineralization,and the activities of various enzymes in relation to nitrate leaching and root distribution in a slurry-amended grassland

High rates of cattle slurry application induce NO _inf3 ^sup- leaching from grassland soils. Therefore, field and lysimeter trials were conducted at Gumpenstein (Austria) to determine the residual effect of various rates of cattle slurry on microbial biomass, N mineralization, activities of soil enzymes, root densities, and N leaching in a grassland soil profile (Orthic Luvisol, sandy silt, pH 6.6). The cattle slurry applications corresponded to rates of 0, 96, 240, and 480 kg N ha^-1. N leaching was estimated in the lysimeter trial from 1981 to 1991. At a depth of 0.50 m, N leaching was elevated in the plot with the highest slurry application. In October 1991, deeper soil layers (0–10, 10–20, 20–30, 30–40, and 40–50 cm) from control and slurry-amended plots (480 kg N ha^-1) were investigated. Soil biological properties decreased with soil depth. N mineralization, nitrification, and enzymes involved in N cycling (protease, deaminase, and urease) were enhanced significantly (P<0.05) at all soil depths of the slurry-amended grassland. High rates of cattle slurry application reduced the weight of root dry matter and changed the root distribution in the different soil layers. In the slurry-amended plots the roots were mainly located in the topsoil (0–10 cm). As a result of this study, low root densities and high N mineralization rates are held to be the main reasons for NO _inf3 ^sup- leaching after heavy slurry applications on grassland.     

The contribution of sorbed sodium and calcium to the self-diffusion of these cations in soils with different clay mineralogies

Self-diffusion coefficients of sodium and calcium were measured on a range of moist subsoils. The ratio of concentrations of each isotope in the liquid phase and on the surface at the water content of the diffusion run was obtained from both the extrapolation of ratios measured at a range of soil:solution ratios, and, where possible, by measurement on expressed soil solution.
The diffusion coefficients were considerably greater than would be predicted if only the liquid phase contributed to diffusion. Surface phase impedance factors, f _s, were calculated for each soil. f _s for sodium was between 1/5 and 1/2 of the liquid phase impedance factor, f _L; f _s for calcium was between 1/9 and 1/20 of f _L. Values of f _s were not obviously related to the clay mineralogy, the proportion of internal to external cation adsorption, the volumetric water content, or the pH.     

Removal of polycyclic aromatic hydrocarbons from soil amended with biosolid or vermicompost in the presence of earthworms (Eisenia fetida)

Earthworms burrow through the soil thereby accumulating many lipophilic organic pollutants from the surrounding environment, so they could be used to remove polycyclic aromatic hydrocarbons (PAHs) from soil. Sterilized and unsterilized soil was contaminated with phenanthrene (Phen), anthracene (Anth) and benzo[a]pyrene (BaP), with or without added Eisenia fetida and biosolid or vermicompost. Concentrations of PAHs were monitored in soil and earthworms for 70 days. Removal of PAHs increased in soil with earthworms added as 91% of Anth, 16% BaP and 99% Phen was dissipated compared to 42%, 3% and 95% in unamended soil. The microorganisms in the gut of the earthworm contributed to PAHs removal and 100% of Phen, 63% of Anth and 58% of BaP was removed from sterilized soil with E. fetida added. Biosolid and to lesser extent vermicompost accelerated removal of PAHs from soil. Applying earthworms to a contaminated site might be an environmentally friendly way to remove hydrocarbons from soil. However, a limitation might be the cost of the large amounts of earthworms required to remove PAHs from soil and the necessity to supply them with sufficient substrate while maintaining the water content of the soil high enough for their normal functioning.     

Analysis of metal cations and inorganic anions in olive oil mill waste waters by atomic absorption spectroscopy and ion chromatography. Detection of metals bound mainly to the organic polymeric fraction

Metal cations were quantitatively detected by atomic absorption spectrometry in samples of olive oil mill waste waters obtained by a pressure process (omww(1)) (K, 17.1; Mg, 2.72; Ca, 2.24; Na, 0.40; Fe, 0.123; Zn, 0.0630; Mn, 0.0147; Cu, 0.00860 g L(-)(1)) and a centrifugation process (omww(2)) (K, 9.80; Mg, 1.65; Ca, 1.35; Na, 0. 162; Fe, 0.0330; Zn, 0.0301; Mn, 0.00910; Cu, 0.00980 g L(-)(1)). The inorganic anions, determined in the same samples by ion chromatography, proved to be Cl(-), H(2)PO(4)(-), F(-), SO(4)(2)(-), and NO(3)(-) (1.61, 1.05, 0.66, 0.52, and 0.023 g L(-)(1), respectively, in omww(1) and 0.61, 0.40, 0.25, 0.20, and 0.0090 g L(-)(1), respectively, in omww(2)). Most of the metal cations were revealed to be bound to the omww organic polymeric fraction (opf), composed of polysaccharides, phenol polymers, and proteins. Opf relative molecular weight was substantially estimated in the range between 1000 and 30000 Da for approximately 75% and in the range from 30000 to 100000 Da for approximately 25%. The free residual cations pool proved to be neutralized by the inorganic counteranions. Finally, the possible exploitation of this material in agriculture and in environmental biotechnology processes is also discussed in the light of its chemical and biochemical oxygen demand parameters.     

The application of double-layer theory to drainage, drying and wetting, and the Gapon Exchange constant in a soil with mono- and divalent cations

Classical double‐layer theory is adapted to consider drainage under gravity, air‐drying, rewetting with distilled water or with solution, and cation exchange when the double‐layer is under a very small retaining pressure or matric potential. In this study, the solid system retains its geometry and the double‐layers are either bounded by an air–water interface or are restricted by the solid geometry. The model as presented is suitable for PCs but is restricted to mono‐ and divalent cations in the presence of a monovalent anion. Representative results for three surface charge densities, three ionic strengths and three ratios of mono‐ to divalent cations are presented. During drainage, the proportion of monovalent cations increases slightly, the ambient anion concentration decreases, whereas the ionic ratio is relatively constant. During drying by evaporation, the proportion of monovalent cations decreases markedly, whereas the anion concentration and the ionic ratio both increase in the ambient solution. These patterns affect the behaviour of roots and organisms in the soil. The Gapon Exchange constant is found to vary with the initial composition of the double‐layer and with the composition of the added solution, but for each combination it tends to an equilibrium value as the volume of the added solution increases. The value of the constant is sensitive to the charge density of the clay surface; the greater the charge density the smaller is the Gapon Exchange constant, suggesting that it should be referred to as the Gapon parameter rather than the Gapon constant. The limitations of the classical theory are discussed in relation to the results obtained.     

Synergistic inhibition of the growth of suspension cultured tobacco cells by simultaneous treatment with cadmium and arsenic in relation to phytochelatin synthesis

Simultaneous treatments with Cd and arsenic (arsenite and arsenate) led to the synergistic growth inhibition of tobacco (Nicotiana tabacum cv. BY-2) cells. Cd contents in cells increased by co-treatment with arsenic for 24 h. The amount of total phytochelatins (PCs) per unit of Cd in the cells treated with Cd and arsenate was lower than that in the cells treated with Cd alone. Simultaneous treatments with Cd and arsenic promoted the induction of the biosynthesis of (γ-Glu-Cys)₂-Gly and inhibited the induction of the biosynthesis of (γ-GluCys)₃-Gly and (γ-Glu-Cys)₄-Gly, compared with the treatment with Cd alone. Consequently, since the inhibition of PC biosynthesis led to the increase of the cellular concentration of putative ionic (= toxic) Cd, cell growth was inhibited synergistically by simultaneous treatments with Cd and arsenic. In addition, based on the results showing that buthionine sulfoximine increased the sensitivity to arsenite and arsenate, that PC biosynthesis was induced by treatment with arsenite or arsenate, it is suggested that glutathione and/or its metabolic products such as PCs are involved in arsenic tolerance.     

Measuring the bioavailability of polychlorinated biphenyls to earthworms in soil enriched with biochar or activated carbon using triolein-embedded cellulose acetate membrane

Purpose

Polychlorinated biphenyls (PCBs) are persistent soil contaminants that resist biodegradation and present serious risks to living organisms. The presence of biochar in soils can lower the availability of PCBs to biota. In this study, the effect of biochar enrichment in soils on bioaccumulation of PCBs was investigated.

Materials and methods

We applied two types of biochar including pine needle biochar (PC) and wheat straw biochar (WC), and an activated carbon (AC) to soil (2 % w/w) and employed two alternative methods to quantified rates of bioaccumulation: a living bioassay (using earthworm, Eisenia fetida, as a model organism) and a triolein-embedded cellulose acetate membrane (TECAM).

Results and discussion

Our results show that the application of biochar or AC greatly reduced the uptake of PCBs (particularly less-chlorinated PCBs) by earthworms (the reduction in total PCBs concentration was up to 40.0 and 49.0 % for PC and WC treatments, while 71.6 % for AC application). We found that the bioaccumulation factors (BAFs) for PCBs in the earthworms in biochar/AC-enriched soils were strongly correlated with O:C ratio of the biochar/AC (R ²?=?0.998, p?<?0.05). We observed that BAFs increased at log K _OW below 6.3 and decreased at log K _OW values greater than 6.3. We demonstrated that the concentration of PCBs in TECAM membranes were positively correlated with the concentration of PCBs earthworms in soil.

Conclusions

TECAM offers an efficient and cost-effective method for predicting the bioavailability of PCBs in field-contaminated soils undergoing sorbent-based remediation.

     

Determination of origin of Atlantic salmon (Salmo salar): the use of multiprobe and multielement isotopic analyses in combination with fatty acid composition to assess wild or farmed origin

Variability within the stable isotope ratios in various lipidic fractions and the fatty acid composition of muscle oil has been analyzed for a large sample (171 fish) of wild and farmed Atlantic salmon ( Salmo salar) from 32 origins within Europe, North America, and Tasmania. Sampling was extended over all seasons in 2 consecutive years and included fish raised by different practices, in order to maximize the range of variation present. It is shown that two readily measured parameters, delta 15N measured on choline and delta18 O measured on total oil, can be successfully used to discriminate between fish of authentic wild and farmed origin. However, the certainty of identification of mislabeling in market-derived fish is strengthened by including the percentage of linoleic acid C18:2n-6 in the lipidic fraction. Thus, several apparent misidentifications were found. The combination of these three analytical parameters and the size of the database generated makes the method practical for implementation in official laboratories as a tool of labeling verification.