Speciation of cadmium in seawater — a direct voltammetric approach

The present report deals with differential pulse anodic stripping voltammetry (DPASV) applied for the analysis of cadmium in open ocean seawater. Evaluation of different Cd species can generate information about distribution and speciation of Cd in the open ocean. Distribution of Cd was investigated in surface waters of the Atlantic Ocean over a wide geographical range as well as in the water column. Surface water sampling on board the research vessel Polarstern was performed from the bow boom of the ship as well as with a snorkel system which allowed continuous sample-taking. Two different Cd species could be differentiated in the voltammograms. UV-irradiation experiments allowed the identification of an inorganic and organic Cd form, the latter caused by the association between Cd and organic matter as e.g. humic substances (HS). Atlantic ocean surface seawater normally contains between 2 and 4 ng organically complexed Cd/kg and no detectable inorganic Cd. Some areas however showed readings of up to 14 ng inorganic Cd/kg in addition. Water column samples exhibited an enrichment of inorganic Cd by depth. Occurrence of inorganic Cd at the surface could be related to specific oceanographical conditions. Together with analytical results of trace metal contents in the particulate phases of surface seawater, new aspects could be established about the biogeochemical cycling of Cd in the sea.     

Density functional study of the electric hyperfine interactions and the redox-structural correlations in the cofactor of nitrogenase. Analysis of general trends in (57)Fe isomer shifts

The influence of the interstitial atom, X, discovered in a recent crystallographic study of the MoFe protein of nitrogenase, on the electric hyperfine interactions of (57)Fe has been investigated with density functional theory. A semiempirical theory for the isomer shift, delta, is formulated and applied to the cofactor. The values of delta for the relevant redox states of the cofactor are predicted to be higher in the presence of X than in its absence. The analysis strongly suggests a [Mo(4+)4Fe(2+)3Fe(3+)] oxidation state for the S = 3/2 state M(N). Among C(4-), N(3-), and O(2-), oxide is found to be the least likely candidate for X. The analysis suggests that X should be present in the cofactor states M(OX) and M(R) as well as in the alternative nitrogenases. The calculations of the electric field gradients (EFGs) indicate that the small values for DeltaE(Q) in M(N) result from an extensive cancellation between valence and ligand contributions. X emerges from the analysis of the hyperfine interactions as an ionically bonded species. Its major effect is on the asymmetry parameters for the EFGs at the six equatorial sites, Fe(Eq). A spin-coupling scheme is proposed for the state [Mo(4+)4Fe(2+)3Fe(3+)] that is consistent with the measured (57)Fe A-tensors and DeltaE(Q) values for M(N) and identifies the unique site exhibiting the small A value with the terminal Fe site, Fe(T). The optimized structure of a cofactor model has been calculated for several oxidation states. The study reveals a contraction in the average Fe-Fe distance upon increasing the number of electrons stored in the cluster, in accord with extended X-ray absorption fine structure studies. The reliability of the adopted methodology for predicting redox-structural correlations is tested for cuboidal [4Fe-4S] clusters. The calculations reveal a systematic increase in the S...S sulfide distances, in quantitative agreement with the available data. These trends are rationalized by a simple electrostatic model.     

Determination of Arsenic Species in Fish Oil After Acid Digestion

Arsenic speciation is of increasing interest to the food industry, as concerns about high total arsenic concentrations in food can often be alleviated to a great extent if the ratio of toxic, less toxic and non-toxic arsenic compounds in the sample is known. The lipid matrix of fish oil is a challenge in the determination of arsenic species, as current methods for this type of analysis require the analyte to be water-soluble. In this study, two sample preparation techniques were applied. One the one hand water-soluble species were extracted with methanol/water, on the other, acid digestion was applied to release lipid-soluble arsenic compounds into the aqueous phase. Ion chromatography – inductively coupled plasma mass spectrometry (IC-ICP-MS) was used for separation and sensitive element-specific detection of arsenic compounds. Additional experiments, including alkaline hydrolysis, were carried out to find out more about the type of lipids arsenic is bound to in fish oil. Up to eight different arsenic species were detected and quantified in fish oil with dimethylarsinate being the major compound both in the aqueous extract and in the acid digest. No inorganic arsenic was detected in the aqueous extract, and the maximum concentration of arsenate determined in the acid digest was 0.05 μg g⁻¹. The total arsenic concentration determined by ICP-MS ranged from <0.1 to 5 μg g⁻¹. With regard to the mass balance, approximately 1% of the total arsenic content was extractable with methanol/water, whereas the sum of arsenic species quantified after acid digestion yielded 85–100% of the total arsenic content. It was confirmed that the large fraction of arsenic in fish oil not extractable on an aqueous basis consists of organoarsenic compounds. This new approach in sample preparation makes the complete characterization of the arsenic content in the sample possible with regard to the respective species, providing necessary information required for risk assessment.     

Mössbauer study of the three-coordinate planar Fe(II) thiolate complex [Fe(SR)(3)](-) (R = C(6)H(2)-2,4,6-tBu(3)): model for the trigonal iron sites of the MoFe(7)S(9):homocitrate cofactor of nitrogenase

The cofactor (M-center) of the MoFe protein of nitrogenase, a MoFe(7)S(9):homocitrate cluster, contains six Fe sites with a (distorted) trigonal sulfido coordination. These sites exhibit unusually small quadrupole splittings, Delta E(Q) approximately 0.7 mm/s, and isomer shifts, delta approximately 0.41 mm/s. M?ssbauer and ENDOR studies have provided the magnetic hyperfine tensors of all iron sites in the S = 3/2 state M(N). To assess the intrinsic zero-field splittings and hyperfine parameters of the cofactor sites, we have studied with M?ssbauer spectroscopy two salts of the three-coordinated Fe(II) thiolate complex [Fe(SR)(3)](-) (R = C(6)H(2)-2,4,6-tBu(3)). One of the salts, [Ph(4)P][Fe(SR)(3)] x 2MeCN x C(7)H(8), 1, has a planar geometry with idealized C(3h) symmetry. This S = 2 complex has an axial zero-field splitting with D = +10.2 cm(-1). The magnetic hyperfine tensor components A(x) = A(y) = -7.5 MHz and A(z) = -29.5 MHz reflect an orbital ground state with d(z(2)) symmetry. A(iso) = (A(x) +A(y) +A(z))/3 = -14.9 MHz, which includes the contact interaction (kappa P = -21.9 MHz) and an orbital contribution (+7 MHz), which is substantially smaller than A(iso) approximately -22 MHz of the tetrahedral Fe(II)(S-R)(4) sites of both rubredoxin and [PPh(4)](2)[Fe(II)(SPh)(4)]. The largest component of the electric field gradient (EFG) tensor is negative, as expected for a d(z(2)) orbital. However, Delta E(Q) = -0.83 mm/s, which is smaller than expected for a high-spin ferrous site. This reduction can be attributed to a ligand contribution, which in planar complexes provides a large positive EFG component perpendicular to the ligand plane. The isomer shift of 1, delta = 0.56 mm/s, approaches the delta-values reported for the six trigonal cofactor sites. The parameters of 1 and their importance for the cofactor cluster of nitrogenase are discussed.     

Calculation of the transport properties of carbon dioxide. III. Volume viscosity, depolarized Rayleigh scattering, and nuclear spin relaxation

Transport properties of pure carbon dioxide have been calculated from the intermolecular potential using the classical trajectory method. Results are reported in the dilute-gas limit for volume viscosity, depolarized Rayleigh scattering, and nuclear spin relaxation for temperatures ranging from 200 to 1000 K. Three recent carbon dioxide potential energy hypersurfaces have been investigated. Calculated values for the rotational collision number for all three intermolecular surfaces are consistent with the measurements and indicate that the temperature dependence of the Brau-Jonkman correlation is not applicable for carbon dioxide. The results for the depolarized Rayleigh scattering cross section and the nuclear spin relaxation cross section show that calculated values for the generally more successful potentials differ from the observations by 9% at about 290 K, although agreement is obtained for nuclear spin relaxation at about 400 K.     

Theoretical analysis of the three-dimensional structure of tetrathiolato iron complexes

The three-dimensional structures of a number of [M(SR)(4)](n-) complexes, where M is a 3d transition metal and R is an alkyl or aryl group, have been analyzed using density functional theory (DFT). Special attention is paid to the Fe(II)/Fe(III) mimics of rubredoxin. The Fe(II) model complex [Fe(SCH(3))(4)](2-) has an equilibrium conformation with D2d symmetry. The DFT energy has been decomposed into contributions for ligand-ligand and metal-ligand interactions. The latter contribution is analyzed with the angular overlap model (AOM) and constitutes the dominant stereospecific interaction in the Fe(II) complex. The sulfur lone-pair electrons exert anisotropic pi interactions on the 3d(6) shell of Fe(II), which are controlled by the torsion angles, omega(i), for the rotations of the S(i)-C(beta) bonds around the Fe-S(i) axes. In contrast, the pi interactions acting on the high-spin 3d(5) shell of Fe(III) are isotropic. As a consequence, the stereochemistry of the Fe(III) complexes is determined by the Coulomb repulsions between the ligands and has S(4) symmetry. The electrostatic repulsions between the lone pairs of the sulfurs are an essential component of the ligand-ligand interaction. The lone-pair repulsions distort the 90 degree angle SFeS' angles (delta + delta(t)) and give rise to a correlation between delta and omega, which is confirmed by crystallographic data. Both the Fe(II) and Fe(III) complexes exhibit structural bistability due to the presence of low-lying equilibrium conformations with S(4) symmetry in which the complex can be trapped by the crystalline host.     

Benefits of high resolution IC-ICP-MS for the routine analysis of inorganic and organic arsenic species in food products of marine and terrestrial origin

A recently developed and validated method for simultaneous determination of 17 inorganic and organic arsenic compounds in marine biota has been successfully applied to routine analysis of different food products, including fish, shellfish, edible algae, rice, and other types of grain. During one year, approximately 250 food samples were analyzed, mostly fish and rice. Long-term stability and robustness of the system was observed and reproducible results for certified reference materials were ensured by means of control charts. The separation was performed by ion-pair chromatography on an anion-exchange column to separate anionic, neutral, and cationic arsenic species in one chromatographic run. Hyphenation to ICP–MS allowed element-specific and sensitive detection of the different arsenic species with a detection limit as low as 8 ng As L^–1 in the sample extract, which is equivalent to 2 ng As g^–1 in the original sample. Special emphasis was laid on the analysis of marine algae and rice samples. These food types can contain elevated levels of the very toxic inorganic arsenic species (up to 90% in rice) and therefore are the focus of interest in the food industry. In marine algae, inorganic arsenic was mainly present as arsenate whereas in rice arsenite predominated.     

Carbon nanotube composite coated platinum electrode for detection of Cr(III) in real samples

This paper demonstrates the application of composite multi-walled carbon nanotube (MWNT) polyvinylchloride (MWNT-PVC) based on 1,5-diphenylcarbazide as chromium ionophore in potentiometric measurement. The sensor shows a good Nernstian slope of 19.52 ± 0.40 mV/decade in a wide linear range concentration of 6.3 × 10⁻⁸ to 1.0 × 10⁻² M for Cr(NO₃)₃. The detection limit of this electrode was found to be 3.2 × 10⁻⁸ M of Cr(NO₃)₃ and is applicable in a pH range of 3.0-6.8. It has a short response time of about 10 s. This chromium electrode has a good selectivity over 16 various metal ions. The practical analytical utility of this electrode was demonstrated by measurement of Cr(III) in drinking water and mineral water samples without any serious preliminary pre-treatment and chromium in multivitamin.     

Development and characterization of hydroquinone-loaded nanofiber for topical delivery: effect of chitosan

Hydroquinone (HQ) loaded polymer solution was electrospun for its topical application. Nanofibers were then investigated in terms of stability, drug release, and antifungal activity. The effect of chitosan (CS) was investigated on the viscosity, stability, drug release, and antifungal activity of the developed formulation. Results indicate a significantly stable HQ-loaded nanofiber formulation. The addition of CS caused hydration of the drug delivery system and enhanced drug release but reduced its stability. HQ-loaded nanofiber mat showed significant antifungal activity, however, there was no inhibition zone in samples containing CS.