Lead exposure does not affect baseline and induced innate immunity in quails.

Lead (Pb) is one of the most common metals found in ecosystems in elevated concentrations derived mainly from anthropogenic activities. Pb toxicity is of special concern in birds due to its capacity for bioaccumulation in the liver, bones, and kidneys causing physiological disruptions. Such disruptions can be lethal in a few days after Pb acute intoxication and they are associated with several million deaths of birds. Moreover, Pb may work as an immunosuppressant as it affects the cell-mediated and humoral immune responses, including components of the acute-phase response (APR). We (1) examined the effects of Pb contamination on the innate immune system, body mass, and food intake of Japanese quails (Coturnix coturnix japonica), and (2) evaluated the effects of Pb on its APR after exposing the animals to Pb acetate in drinkable water during 7 days. We found that Pb contamination increased the number of circulating white blood cells (WBCs), but no effect was found on body mass, food intake, the heterophil/lymphocyte (H/L) ratio, and haptoglobin (Hp) concentration. When Pb-exposed birds were injected with lipopolysaccharide from Escherichia coli to activate the APR, they had a negative body mass ratio, reduced food intake, and increased the number of WBCs, the H/L ratio, and the Hp concentration. We conclude that Pb exposure at this dose did not affect baseline values of the constitutive response and that it did not affect the APR of quails, but commend for further studies testing the effect of different Pb doses.

Intraspecific variation of trace elements in the kelp gull (Larus dominicanus): influence of age, sex and location.

Hepatic tissue of Larus dominicanus sampled on the coastline of the state of Santa Catarina in Brazil between October 2016 and May 2018 was used to evaluate intraspecific trends and spatial distribution of essential trace elements (Mn, Co, Cu, Zn, Mo and Cr) and non-essential trace elements (As, Pb, Cd, Hg, Ba and V). Principal Component Analysis (PCA) indicated differences in the bioaccumulation of trace elements between female adults and male adults, differences to sex and age were indicated by Kruskal-Wallis test. Heat maps suggest hot spots in locals with high concentration of trace elements in liver of Larus dominicanus. In general, the concentration of trace elements were comparable with values reported in other studies carried out for this species in South America and other regions of the world. The heat maps showed to be a promising tool to identify influences of the locality on bioaccumulation of trace elements in Larus dominicanus.

Metal speciation of the Paraopeba river after the Brumadinho dam failure.

On January 25, 2019, a tailings dam at the Córrego do Feijão iron ore mine (Brumadinho, Minas Gerais, southern Brazil) ruptured and released ~12 million m3 of mine tailings into the Paraopeba River, which is an important source of drinking water to a populous region. While water potability due to a strong increase in turbidity has been well documented, possible effects of metal contamination are yet to be addressed. We investigated the speciation of metals in the river water and desorption of metals from sediments as a means of supporting risk assessment, using the diffusive gradient in thin films (DGT) technique, desorption experiments and chemical speciation calculations. The results of the in-situ DGT monitoring revealed that the labile concentrations of metals were low in relation to the respective total and dissolved concentrations. Chemical speciation calculations showed that the heavy metals were not stable in the Paraopeba River. The desorption experiments suggested that sediments may release a limited amount of As and Cu, but large amounts of Mn into the river water. Higher concentrations of Fe and Mn indicated a possible association with the impact of mine tailings. In general, the total metal concentrations during the rainy season were higher than those during the dry season, whereas the reverse was generally the case for labile forms. This pattern reveals that metal speciation is intrinsically dependent on the seasonal variation of the hydrological conditions.

Corrigendum: A Nanostructured Lipid System to Improve the Oral Bioavailability of Ruthenium(II) Complexes for the Treatment of Infections Caused by Mycobacterium tuberculosis.

[This corrects the article DOI: 10.3389/fmicb.2018.02930.].

Residual biomass of coffee as a binding agent in diffusive gradients in thin-films technique for Cd, Cu, Ni, Pb and Zn measurement in waters.

Spent coffee grounds (SCG) immobilized in agarose gel are proposed as a novel binding agent for application in the Diffusive Gradients in Thin films (DGT) technique for the determination of Cd, Cu, Ni, Pb and Zn in waters. The SCG-agarose gel was characterized by Scanning Electron Microscopy, Energy Dispersive X-ray Spectrometry and Porosimetry by nitrogen adsorption. Elution of analytes from the binding agent was effectively performed with 2 mol L-1 HCl. The effects of key DGT parameters (e.g. immersion time, ionic strength and pH) were evaluated with a deployment of DGT devices (DGT-SCG) in synthetic solutions with ionic strengths between 0.005 mol L-1 and 0.1 mol L-1 and within a pH range of 3.5-8.0. The results were in excellent agreement with the predicted theoretical curve for mass uptake. Consistent results were found for solutions with ionic strengths between 0.005 mol L-1 and 0.1 mol L-1 and within a pH range of 3.5-8.0. The DGT-SCG performance was also evaluated in two spiked river water samples (Corumbataí and Piracicaba river) with satisfactory uptake values (CDGT-SCG/Csol) between 0.74 and 1.53. The proposed DGT-SCG opens opportunities for using residual biomass as binding phase in the DGT technique, showing low costs in production and complying with "green" technology approaches.

Corrigendum: A Nanostructured Lipid System to Improve the Oral Bioavailability of Ruthenium(II) Complexes for the Treatment of Infections Caused by Mycobacterium tuberculosis.

[This corrects the article DOI: 10.3389/fmicb.2018.02930.].

Determination of in vitro absorption in Caco-2 monolayers of anticancer Ru(II)-based complexes acting as dual human topoisomerase and PARP inhibitors.

Due to their unique and versatile biochemical properties, ruthenium-based compounds have emerged as promising anticancer agents. Previous studies showed that three ruthenium(II) compounds: [Ru(pySH)(bipy)(dppb)]PF6 (1), [Ru(HSpym)(bipy)(dppb)]PF6 (2) and Ru[(SpymMe2)(bipy)(dppb)]PF6 (3) presented anticancer properties higher than doxorubicin and cisplatin and acted as human topoisomerase IB (Topo I) inhibitors. Here, we focused our studies on in vitro intestinal permeability and anticancer mechanisms of these three complexes. Caco-2 permeation studies showed that 1 did not permeate the monolayer of intestinal cells, suggesting a lack of absorption on oral administration, while 2 and 3 permeated the cells after 60 and 120 min, respectively. Complexes 2 and 3 fully inhibited Topo II relaxation activity at 125 µM. In previously studies, 3 was the most potent inhibitor of Topo I, here, we concluded that it is a dual topoisomerase inhibitor. Moreover, it presented selectivity to cancer cells when evaluated by clonogenic assay. Thus, 3 was selected to gene expression assay front MDA-MB-231 cells from triple-negative breast cancer (TNBC), which represents the highly aggressive subgroup of breast cancers with poor prognosis. The analyses revealed changes of 27 out of 84 sought target genes. PARP1 and PARP2 were 5.29 and 1.83 times down-regulated after treatment with 3, respectively. PARPs have been attractive antitumor drug targets, considering PARP inhibition could suppress DNA damage repair and sensitize tumor cells to DNA damage agents. Recent advances in DNA repair studies have shown that an approach that causes cell lethality using synthetic PARP-inhibiting drugs has produced promising results in TNBC.

A Nanostructured Lipid System to Improve the Oral Bioavailability of Ruthenium(II) Complexes for the Treatment of Infections Caused by Mycobacterium tuberculosis.

Tuberculosis (TB) is an infectious, airborne disease caused by the bacterium Mycobacterium tuberculosis that mainly affects the lungs. Fortunately, tuberculosis is a curable disease, and in recent years, death rates for this disease have decreased. However, the existence of antibiotic-resistant strains and the occurrence of co-infections with human immunodeficiency virus (HIV), have led to increased mortality in recent years. Another area of concern is that one-third of the world's population is currently infected with M. tuberculosis in its latent state, serving as a potential reservoir for active TB. In an effort to address the failure of current TB drugs, greater attention is being given to the importance of bioinorganic chemistry as an ally in new research into the development of anti-TB drugs. Ruthenium (Ru) is a chemical element that can mimic iron (Fe) in the body. In previous studies involving the following heteroleptic Ru complexes, [Ru(pic)(dppb)(bipy)]PF6 (SCAR1), [Ru(pic)(dppb)(Me-bipy)]PF6 (SCAR2), [Ru(pic)(dppb)(phen)]PF6 (SCAR4), cis-[Ru(pic)(dppe)2]PF6 (SCAR5), and [Ru(pic)(dppe)(phen)]PF6 (SCAR7), we observed excellent anti-TB activity, moderate cell-toxicity, and a lack of oral bioavailability in an in vivo model of these complexes. Therefore, the objective of this study was to evaluate the toxicity and oral bioavailability of these complexes by loading them into a nanostructured lipid system. The nanostructured lipid system was generated using different ratios of surfactant (soybean phosphatidylcholine, Eumulgin®, and sodium oleate), aqueous phase (phosphate buffer with a concentration of 1X and pH 7.4), and oil (cholesterol) to generate a system for the incorporation of Ru(II) compounds. The anti-TB activity of the compounds was determined using a microdilution assay with Resazurin (REMA) against strains of M. tuberculosis H37Rv and clinical isolates resistant. Cytotoxicity assay using J774.A1 cells (ATCC TIB-67) and intra-macrophage activity were performed. The oral bioavailability assay was used to analyze blood collected from female BALB/C mice. Plasma collected from the same mice was analyzed via inductively coupled plasma mass spectrometry (ICP-MS) to quantify the number of Ru ions. The complexes loaded into the nanostructured lipid system maintained in vitro activity and toxicity was found to be reduced compared with the compounds that were not loaded. The complexes showed intra-macrophagic activity and were orally bioavailable.

Not Good, but Not All Bad: Dehydration Effects on Body Fluids, Organ Masses, and Water Flux through the Skin of Rhinella schneideri (Amphibia, Bufonidae).

Because of their permeable skin, terrestrial amphibians are constantly challenged by the potential risk of dehydration. However, some of the physiological consequences associated with dehydration may affect aspects that are themselves relevant to the regulation of water balance. Accordingly, we examined the effects of graded levels of dehydration on the rates of evaporative water loss and water absorption through the skin in the terrestrial Neotropical toad, Rhinella schneideri. Concomitantly, we monitored the effects of dehydration on the mass of visceral organs; hematocrit and hemoglobin content; plasma osmolality; and plasma concentration of urea, sodium, chloride, and potassium. We found that dehydration caused an increase in the concentration of body fluids, as indicated by virtually all the parameters examined. There was a proportional change in the relative masses of visceral organs, except for the liver and kidneys, which exhibited a decrease in their relative masses greater than the whole-body level of dehydration. Changes-or the preservation-of relative organ masses during dehydration may be explained by organ-specific physiological adjustments in response to the functional stress introduced by the dehydration itself. As dehydration progressed, evaporative water loss diminished and water reabsorption increased. In both cases, the increase in body fluid concentration associated with the dehydration provided the osmotic driver for these changes in water flux. Additionally, dehydration-induced alterations on the cutaneous barrier may also have contributed to the decrease in water flux. Dehydration, therefore, while posing a considerable challenge on the water balance regulation of anurans, paradoxically facilitates water conservation and absorption.

In situ speciation of uranium in treated acid mine drainage using the diffusion gradients in thin films technique (DGT).

The exchange membranes P81 and DE81 and Chelex-100 resin were used to perform in situ speciation of uranium in treated acid mine drainage at the Osamu Utsumi mining site, Poços de Caldas city, Southeast Brazil. To investigate possible chemical modifications in the samples during analysis, the three ligands were deployed in situ and in a laboratory (in lab). The results obtained in situ were also compared to a speciation performed using Visual MINTEQ software. Chelex-100 retained total labile U for a period of up to 48 h. The labile U fraction determined by Chelex 100 ranged from 107 ± 6% to 147 ± 44% in situ and from 115 ± 22% to 191 ± 5% in lab. DE81 retained anionic U species up to 8 h, with labile fractions ranging from 37 ± 2% to 76 ± 3% in situ and 34 ± 12% to 180 ± 17% in lab. P81 exhibited a lower efficiency in retaining U species, with concentrations ranging from 6± 2% to 19± 2% in situ and 3± 2% to 18± 2% in lab. The speciation obtained from MINTEQ suggests that the major U species were UO2OH+, UO2(OH)3-, UO2(OH)2(aq), Ca2UO2(CO3)3(aq), CaUO2(CO3)32-, UO2(CO3)22-, and UO2(CO3)34-. This result is in accordance with the results obtained in situ. Differences concerning speciation and the total and soluble U concentrations were observed between the deployments performed in situ and in the laboratory, indicating that U speciation must be performed in situ.

Novel Zinc(II) Complexes [Zn(atc-Et)2] and [Zn(atc-Ph)2]: In Vitro and in Vivo Antiproliferative Studies.

Cisplatin and its derivatives are the main metallodrugs used in cancer therapy. However, low selectivity, toxicity and drug resistance are associated with their use. The zinc(II) (Zn(II)) thiosemicarbazone complexes [Zn(atc-Et)2] (1) and [Zn(atc-Ph)2] (2) (atc-R: monovalent anion of 2-acetylpyridine N4-R-thiosemicarbazone) were synthesized and fully characterized in the solid state and in solution via elemental analysis, Fourier transform infrared (FTIR), ultraviolet-visible (UV-Vis) and proton nuclear magnetic resonance (¹H NMR) spectroscopy, conductometry and single-crystal X-ray diffraction. The cytotoxicity of these complexes was evaluated in the HepG2, HeLa, MDA-MB-231, K-562, DU 145 and MRC-5 cancer cell lines. The strongest antiproliferative results were observed in MDA-MB-231 and HepG2 cells, in which these complexes displayed significant selective toxicity (3.1 and 3.6, respectively) compared with their effects on normal MRC-5 cells. In vivo studies were performed using an alternative model (Artemia salina L.) to assure the safety of these complexes, and the results were confirmed using a conventional model (BALB/c mice). Finally, tests of oral bioavailability showed maximum plasma concentrations of 3029.50 µg/L and 1191.95 µg/L for complexes 1 and 2, respectively. According to all obtained results, both compounds could be considered as prospective antiproliferative agents that warrant further research.

In situ redox speciation analysis of chromium in water by diffusive gradients in thin films using a DE81 anion exchange membrane.

A method for the in situ redox speciation analysis of chromium in water by the diffusive gradients in thin films (DGT) technique using a DE81 anion exchange membrane was successfully developed. For the selective uptake of Cr(VI), a DGT device containing an anion exchange membrane DE81 (cellulose acetate chromatographic paper) was used (DE81-DGT), while selective uptake of Cr(III) was carried out using DGT devices containing the Chelex-100 resin (Chelex-100-DGT). A correlation coefficient of 0.993 was obtained for the linearity of the immersion curves (mass versus time) using DE81-DGT. The diffusion coefficient values for Cr(VI) through the agarose diffusive layer were equal to 4.89±0.5×10(-6)cm(2)s(-1) and 3.95±0.02×10(-6)cm(2)s(-1) (T=23±1°C, I=0.03molL(-1) NaNO3) were obtained by using diffusion cell and immersion curves, respectively. The retention of Cr(VI) by the DE81 membrane in a synthetic sample and river water was not affected by the pH over a wide range 4-9). Recoveries of Cr(VI) between 90% and 120% from solutions of ionic strength ranging from 0.01 to 0. 5molL(-1) NaNO3 were achieved. Finally, the redox speciation analysis of Cr(III) and Cr(VI) in spiked river water and synthetic samples was performed with recoveries greater than 80% and 87% by using Chelex-100-DGT and DE81-DGT devices, respectively. Those results were in excellent agreement with the diphenylcarbazide spectrophotometric method.

Measurements of labile Cd, Cu, Ni, Pb, and Zn levels at a northeastern Brazilian coastal area under the influence of oil production with diffusive gradients in thin films technique (DGT).

In this work, the ability of the diffusive gradients in thin films technique (DGT) was evaluated for monitoring the concentrations, and estimating the availability, of metals at a northeastern Brazilian coastal area under the influence of oil production. Three sites with an average distance between 0m (EM-1), 100 m (EM-2), and 1,000 m (EM-3) of a submarine outfall-I (Guamaré-RN, Brazil) and another site (GA-1) with an average distance of 12,000 m east of Outfall I, near the city of Galinhos, were studied. DGT units were deployed at the same sites in three campaigns from July, 2010 to June, 2011. Effects on the accuracy of analytical results regarding the deployment time, gel porosity, and thickness were evaluated. There was no difference between the measurements obtained with two sets of DGT devices, those assembled with open or restrictive pore gel, respectively, showing that organic metallic species are not present near the submarine outlet. After 21 day deployments in a region (near Submarine Outfall I) that receives produced waters that have been treated, there was evidence of biofilm formation on DGT membranes. However, it was demonstrated that the biofilm interference with DGT measurements was negligible. Data found in this work show that total concentrations of Cd, Cu, Pb, Ni, and Zn in seawater samples collected at sites GA-1 and EM-1 in two campaigns were below 0.33, 1.67, 0.47, 0.70, 2.86 ng mL(-1) respectively. For the first time, labile levels of Cd, Cu, Pb, Ni, and Zn in an area under the influence of oil production were determined. DGT measurements allowed the verification of the effects of temporal variation on levels of Zn and Ni. There were no effects of spatial variations on levels of Cd, Cu, Ni, Pb, and Zn at the four studied sites, suggesting no contamination of these metals at the northeastern Brazilian coastal area investigated in this work.

Evaluation of Fe uptake and translocation in transgenic and non-transgenic soybean plants using enriched stable (57)Fe as a tracer.

A tracer experiment is carried out with transgenic T (variety M 7211 RR) and non-transgenic NT (variety MSOY 8200) soybean plants to evaluate if genetic modification can influence the uptake and translocation of Fe. A chelate of EDTA with enriched stable (57)Fe is applied to the plants cultivated in vermiculite plus substrate and the (57)Fe acts as a tracer. The exposure of plants to enriched (57)Fe causes the dilution of the natural previously existing Fe in the plant compartments and then the changed Fe isotopic ratio ((57)Fe/(56)Fe) is measured using a quadrupole-based inductively coupled plasma mass spectrometer equipped with a dynamic reaction cell (DRC). Mathematical calculations based on the isotope dilution methodology allow distinguishing the natural abundance Fe from the enriched Fe (incorporated during the experiment). The NT soybean plants acquire higher amounts of Fe from natural abundance (originally present in the soil) and from enriched Fe (coming from the (57)Fe-EDTA during the experiment) than T soybean ones, demonstrating that the NT soybean plants probably absorb higher amounts of Fe, independently of the source. The percentage of newly incorporated Fe (coming from the treatment) was approximately 2.0 and 1.1% for NT and T soybean plants, respectively. A higher fraction (90.1%) of enriched Fe is translocated to upper parts, and a slightly lower fraction (3.8%) is accumulated in the stems by NT plants than by T ones (85.1%; 5.1%). Moreover, in both plants, the Fe-EDTA facilitates the transport and translocation of Fe to the leaves. The genetic modification is probably responsible for differences observed between T and NT soybean plants.

Speciation analysis of inorganic arsenic in river water by Amberlite IRA 910 resin immobilized in a polyacrylamide gel as a selective binding agent for As(V) in diffusive gradient thin film technique.

In this study, a method is proposed for the selective retention of As(V) using diffusive gradient in thin film (DGT) samplers containing a strongly basic anion exchange resin (Amberlite IRA 910) supported on a polyacrylamide gel. In addition, the total arsenic content is determined by ferrihydrite gel discs. Subsequently, the concentration of As(III) was obtained by determining the difference between the total As and As(V). DGT experiments showed linear accumulation of As(V) (up to 280 ng) until a deployment time of 8 h deployment (R(2) > 0.99). The retention of As(V) was appropriate (97.9-112.3%) between pH 5 and 9. For a solution with an ionic strength ranging from 0.001 to 0.05 mol L(-1), the As(V) uptake ranged from 90-120%. The proposed method was applied for the speciation of arsenic in river water. For the analysis of spiked samples collected at the Furnas stream, the recoveries of total arsenic content ranged between 103.9% and 118.8%. However, the recoveries of As(III) and As(V) were 43.3-75.2% and 147.3-153.4%, respectively. These differences were probably because of the oxidation of As(III) to As(V) during deployments. For spiked samples collected at the Ribeirão Claro, the recoveries of dissolved As(III), As(V) and As(T) were 103.1%, 108.0% and 106.3%, respectively. Thus, the DGT technique with Amberlite IRA 910 resin as the binding phase can be employed for the in situ redox speciation of inorganic arsenic.

Determination of in situ speciation of manganese in treated acid mine drainage water by using multiple diffusive gradients in thin films devices.

Acid mine drainage (AMD) is a serious environmental problem that creates acidic solution with high Mn concentrations. The speciation of residual Mn from AMD after an active treatment involving the addition of a neutralizing agent can reliably evaluate the treatment efficiency and provide knowledge of the Mn species being inputted into the environment. The aim of this study was to evaluate the in situ lability and speciation of Mn using the diffusive gradients in thin films (DGT) technique with treated drainage water from a uranium mine (TAMD). DGT devices with different binding phases (Chelex-100 and P81 and DE81 membranes) were used to perform the in situ speciation of Mn. A comparison of the results from deploying DGT in the laboratory and in situ shows that the speciation of Mn in TAMD should be performed in situ. Linear deployment curves (from in situ experiments) indicate that the DGT device containing the Chelex-100 binding phase can be used to evaluate Mn lability in TAMD. The labile Mn fraction (from in situ measurements) obtained using the device containing the Chelex-100 resin ranged from 63 to 81% of the total Mn concentration and, when compared to the speciation obtained using the CHEAQS software, indicated that this device was capable of uptaking the free Mn(2+) and a portion of the MnSO4(aq). The values obtained using the DGT technique were compared to those from on site solid phase extraction, and a good agreement was found between the results. The amount of negative Mn species sampled by DE81 device was insignificant (<1.5%) for all of the sites. Sites containing a relatively small amount of Ca (<40 mg L(-1)) and measured using devices containing the P81 membrane agreed with the concentration predicted by the CHEAQS software for positive Mn species (Mn(2+) and Mn(OH)(+)). Nevertheless, the speciation obtained using the CHEAQS software indicated that the concentrations of positive Mn species were underestimated for sites with relatively high Ca concentrations (>150 mg L(-1)), which take place due to the saturation of binding sites in the P81 membrane.

Use of Saccharomyces cerevisiae immobilized in agarose gel as a binding agent for diffusive gradients in thin films.

A new binding agent, consisting of the yeast Saccharomyces cerevisiae immobilized in agarose, is proposed for use in diffusive gradients in thin films (DGT). Different gel compositions, containing from 4.5% to 20% (m/v) of S. cerevisiae and 1.5-5.0% (m/v) of agarose, were prepared and tested for uptake of Cd(II). For gels containing 20% (m/v) of S. cerevisiae, a mass of 14,900 ng has been attributed as the uptake limit of Cd for each disk. Determination of the Cd retained in the binding agent was readily carried out using a slurry of the agarose-yeast disk introduced directly into the inductively coupled plasma optical emission spectrometer. The performance characteristics of the DGT samplers, which were assembled with the proposed binding agent (25 mm disk containing 20% of S. cerevisiae and 1.5% of agarose) and a diffusive layer of cellulose (chromatographic paper 3MM Chr of 25 mm diameter), were evaluated by measuring the Cd(II) uptake at various pH values and ionic strengths. Very consistent results were found within the pH range 4.5-7.5 and at ionic strengths ≥0.005 molL(-1). The precision of DGT measurements was characterized by relative standard deviations of <8%. No changes in the uptake of Cd(II) were observed in the samplers that were assembled with recently prepared disks or 35-day-old stored disks. The proposed material has been applied to the analyses of river and sea water samples. For determination of Cd(II), excellent agreement between the results obtained from devices assembled with the proposed material and those assembled with conventional material (Chelex-100 resin) were obtained, strongly validating the use of the agarose-yeast gel disk as a new binding agent for DGT.

On-line redox speciation analysis of antimony using l-proline immobilized on controlled pore glass and hydride generation inductively coupled plasma optical emission spectrometry for detection.

L-proline was immobilized on controlled pore glass to study the ability of this material for the separation and preconcentration of Sb(III) and Sb(V). The substrate was packed in a minicolumn and incorporated in a flow injection system. The effluents of the on-line solid phase extraction (before and after elution) were directly coupled to the hydride generation inductively coupled plasma optical emission spectrometry system. The effect of pH, sample (and eluent) volume, flow rates of sample loading and elution on separation of Sb(III) e Sb(V) were evaluated. Our experiments demonstrated that Sb(V) was not retained and it was selectively determined during the loading step, while retained Sb(III) was determined after elution. The proposed system was also used for the selective preconcentration of Sb(III). In this case, a preconcentration factor of 11 and a limit of detection of 90 ng L(-1) for Sb(III) were achieved when 8 mL of sample were loaded into the column. The speciation analysis of inorganic Sb in river water and effluent samples was performed using the proposed method. The values obtained for total Sb (obtained by sum of Sb(III) and Sb(V)) were in good agreement with expected values. Recoveries of Sb(III) and Sb(V) in the river water Standard Reference Material 1640 (from National Institute of Standard and Technology) and spiked river waters were between 83 and 111%.

Use of diffusive gradients in thin films and tangential flow ultrafiltration for fractionation of Al(III) and Cu(II) in organic-rich river waters.

Diffusive gradients in thin films (DGT) and tangential-flow ultrafiltration (TF-UF) were combined for fractionation of Al and Cu in river water containing high content of dissolved organic carbon. A procedure based on ultrafiltration data is proposed to determine diffusion coefficients of the analytes in water samples and model solutions containing both free metal (M) and complex (metal-humic substance). Aiming to evaluate the accuracy of the proposed approach, the DGT results were compared with those from a protocol for determination of labile Al and Cu based on solid phase extraction (SPE). Good agreement between data from DGT and SPE were attained for model solutions. For analysis of real organic-rich water samples, differences between DGT and SPE measurements were consistent with the time-scales of the techniques. The concentration of labile Al determined by DGT were lower than the total dissolved concentrations (determined by inductively coupled plasma mass spectrometry) and exceeded the ultrafiltered concentration, indicating that inorganic Al species (species small enough to pass through 1 kDa membrane) were minor species as compared with Al organic complexes. For both Al and Cu, there were species not measured by DGT as they are not sufficiently labile.