Comparison of the diversity of sulfate-reducing bacterial communities in the water column and the surface sediments of a Japanese meromictic lake

The diversity and abundance of sulfate-reducing bacteria (SRB) were investigated in Lake Suigetsu, a meromictic lake in Japan characterized by a permanent oxycline at a depth between 3 and 8 m separating the aerobic freshwater epilimnion from the anaerobic, saline, sulfidogenic hypolimnion. A quantitative competitive PCR targeting the gene coding for a portion of the α-subunit of dissimilatory sulfite reductase (dsrA) was used to assess the distribution of the SRB in the stratified water column and the surface sediments. The diversity of the SRB communities was assessed using a sequence analysis of the differing dsrA isomers. The dsrA gene copy numbers of SRB in the hypolimnic waters were from 9.6 × 10³ to 7.5 × 10⁵ copies ml⁻¹, whereas higher dsrA copy numbers of SRB were observed in surface sediments, ranging from 1.8–8.1 × 10⁷ copies ml⁻¹ as estimated by competitive PCR. Phylogenetic analysis of the dsrA sequences retrieved from the surface sediments shows most belong to a deeply branching lineage of diverse dsrA sequences not related to any cultured SRB group. In contrast, dsrA sequences found in the oxycline waters were related to sequences of members of the genera Desulfonema, Desulfosarcina, and Dusulfococcus and to sequences of the incomplete oxidizers from the Desulfobulbaceae family. Diversity and abundance of dsrA genes significantly differed between the samples from the oxycline waters and the surface sediments of Lake Suigetsu, indicating habitat-specific SRB communities may contribute to the biogeochemical cycling of carbon and sulfur.     

Ecological Risk Assessment of Sediments in Sydney Harbour,Nova Scotia,Canada

Contamination within sediments of Sydney Harbour (once a major industrial port) were evaluated using a multiple lines-of-evidence (LOE) ecological risk assessment (ERA) approach prior to divestiture of the harbor. The multiple LOE approach included: (1) measurement of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), metals, metalloids, petroleum hydrocarbons(PHCs), and total organic carbon (TOC) concentrations in surface sediments from multiple Sydney Harbour locations; (2) identification and application of sediment quality guidelines (SQGs) from various jurisdictions; (3) comparisons of harbor sediment chemistry against background/reference sediment chemistry; (4) determining number and frequency of exceedances over SQGs; (5) calculating mean probable effect level-quotients (PEL-Qs); (6) PAH forensic source evaluation; (7) review of previous sediment chemistry and biota tissue data; and (8) characterizing benthic habitat at harbor stations. The ERA determined that current sediments exhibited mostly low probability of adverse effects. Furthermore, contaminated sediments exhibiting a high probability of adverse effects were localized to only a few stations within the harbor. Ongoing natural recovery of harbor sediments is likely responsible for attenuating contaminants that historically were higher than those measured in this study and were previously distributed over much wider areas of the harbor. Results suggest that legacy industrial activities and current urban sewage effluents are the major sources of contamination in Sydney Harbour sediments.     

1,1′-Diethyl-2,2′,3,3′,4,4′,5,5′-octamethylferrocenium tetracyanoethylenide, [Fe(C5EtMe4)2][TCNE], a charge-transfer salt magnetic solid with a novel structural motif

1,1′-Diethyl-2,2′,3,3′,4,4′,5,5′-octamethylferrocene has been utilized as a one-electron donor in the synthesis of a tetracyanoethylene charge-transfer salt, [Fe(C₅EtMe₄)₂]⁺[TCNE]⁻. Structural characterization shows that it adopts an arrangement of anions and cations completely different from the usual π stacking seen in analogous decamethylferrocenium compounds. The TCNE radical sits along side of the ferrocene, nearly perpendicular to the planes of the C₅ rings. The nearly square geometry of the TCNE anion creates disorder over two orientations. [Fe(C₅EtMe₄)₂]⁺[TCNE]⁻ is a simple paramagnet exhibiting neither long-range magnetic order nor slow paramagnetic relaxation to the lowest measured temperatures (ca. 1.8 K) as determined by both ac and dc magnetic susceptibility and Mössbauer spectroscopy (ca. 1.3 K).     

Mononuclear and polynuclear halide and nitrate Cu(II) compounds with 1,4,5-triazanaphthalene as a ligand: Characterization, magnetism and X-ray structures

Using the ligand 1,4,5-triazanaphthalene (abbreviated as tan) in combination with Cu(II) salts, three mononuclear compounds, Cu(tan)₂Cl₂ (1), Cu(tan)₂Br₂ (3), Cu(tan)₂(NO₃)₂ (5) and three polynuclear compounds, [Cu(tan)Cl₂]_n (2), [Cu(tan)Br₂]_n (4), [Cu(tan)(NO₃)₂]_n (6) have been synthesized and characterized by UV-Vis, EPR, FTIR and Far-FTIR spectroscopies. The crystal structures of compounds 1, 3, 5 and 6 are reported, as well as that of the dioxane adduct of compound 4, [Cu(tan)Br₂(C₄H₈O₂)](C₄H₈O₂) (4A).The structure of (2) was solved by X-ray powder diffraction. The coordination geometry around the Cu(II) atoms is tetrahedral for (1) and (3), square-pyramidal for (4A) and distorted octahedral for (5) and (6). Magnetic susceptibility measurements on the polynuclear compounds revealed weak antiferromagnetic interactions between the Cu(II) atoms with interaction constants (J) of J = −9.1 and −10.5 cm⁻¹, for 4 and 6, respectively. For compound 2 two options for possible interactions were considered, with interaction constants which vary for J_rung −22.0 to −13.5 cm⁻¹ and J_rail −19.6 to −17.0 cm⁻¹. These figures are discussed in the light of relevant structural parameters and literature.     

Cobalt(II) coordination polymers assembled from polycarboxylate and benzotriazole: Syntheses, structures and physical properties

Hydrothermal reactions of cobalt(II) salt with H₂CAM or H₂SDBA and HBTA in the presence of NaOH afford two interesting coordination polymers, Co₃(CAM)₂(BTA)₂ (1) and Co₃(SDBA)₂(BTA)₂ (2) (H₂CAM = camphoric acid, H₂SDBA = 4,4′-dicarboxybiphenyl sulfone, HBTA = benzotriazole), both of which have been structurally characterized by single-crystal X-ray, elemental analysis, infrared spectroscopy, and thermogravimetric analysis. Complexes 1 and 2 are isostructural and possess two-dimensional covalent network, comprising an unusual linear Co(II) chains of mixed T_d-O_h-T_d geometries. Temperature-dependent magnetic measurements indicate the existence of antiferromagnetic interactions in both 1 and 2.     

Spectroscopic and magnetic properties of diethyl (pyridin-4-ylmethyl)phosphate (4-pmOpe) ligand with perchlorate transition metal salts. Crystal structure of [Cu(4-pmOpe)2(ClO4)2]

The perchlorate M(II) (M = Cu, Ni, Co) complexes with the diethyl (pyridin-4-ylmethyl)phosphate (4-pmOpe) ligand of the composition [M(4-pmOpe)₂ (H₂O)₂](ClO₄)₂ (M = Ni, Co) and [Cu(4-pmOpe)₂(ClO₄)₂] were prepared and studied. The ligand contains two donor atoms, i.e. pyridine nitrogen and phosphoryl oxygen atoms. In particular, the crystal structure of [Cu(4-pmOpe)₂(ClO₄)₂] was determined by the X-ray method. Its structure consists of a one-dimensional polymeric chain in which copper(II) ions are N,O-bridged by two 4-pmOpe organic ligands in a trans arrangement. Two perchlorate ions occupy the fifth and the sixth coordination sites. The Cu?Cu distance is 9.180 Å. The crystal packing is determined by the weak intermolecular C-H?O hydrogen contacts. The coordination compounds were identified and characterized by elemental analysis, spectroscopic and magnetic studies. Spectroscopic and magnetic results of the copper(II) compound are presented in the light of the crystal structure. The magnetic data indicate very weak intra- and interchain magnetic exchange interactions (J^’ = −0.43 and zJ^’ = 0.29 cm⁻¹, respectively). The spectroscopic and magnetic properties of the Co(II) and Ni(II) complexes indicate octahedral and polymeric structure of both compounds in which 4-pmOpe ligand also acts as N,O-bridge between metal ions.     

Boron sources, speciation and its potential impact on health

The behaviour of boron (B) and its fate in the environment remains in many respects obscure. The major B sources and fluxes seem to have been identified, although there are many uncertainties about the magnitude and importance of each; published evaluations vary greatly. Little is known about B speciation of living matter-bearing formations, i.e. soils, natural waters, and sediments. Many authors suppose that B in nature occurs only as oxo-compounds, although, natural inorganic and organic B compounds and complexes have been described. Moreover, the most common approach to B biogeochemistry in terms of inorganic B compounds (as boric acid and borates) seems to oversimplify the matter. Data on the physiological functions of B are fragmentary and often contradictory. Some data exists on endemic symptoms and diseases among humans and grazing cattle that are supposedly triggered by B abundance in the natural environment. Unfortunately, the published data are scarce and vague. In this paper, we review the up-to date references on B sources, turnover, and speciation in the environment and the element potential impact on health.     

Symmetrical linear Co3 chains cocooned by two polypyridylamide ligands: How do they compare to open chains?

Two extended metal atom chain (EMAC) compounds having a symmetrical Co₃⁶⁺ metal chain encapsulated by two N,N′-bis[(6′-pyrid-2″-yl)aminopyrid-2′yl]-bismethyl-2,6-diaminopyridinate (mpeptea) ligands have been prepared in good yield, and they have been structurally characterized by X-ray crystallography, magnetic and electrochemical measurements and spectroscopic techniques. For the EMAC [Co₃(mpeptea)₂]Cl₂ two solvates have been crystallized. Anion exchange has also allowed isolation of [Co₃(mpeptea)₂](BPh₄)₂. In these three species the Co₃⁶⁺ units are cocooned within two polypyridine ligands having nine nitrogen atoms although only seven of these coordinate to the metal centers. The cations [Co₃(mpeptea)₂]²⁺ are similar and have Co ··· Co separations of ca. 2.3 Å at 213 K. These distances are consistent with partial bond formation between Co atoms. Electrochemical measurements show a unique one-electron oxidation process that differs from that in open chain species which show two reversible oxidation processes. At 300 K, the χT value is 7.32 emu K mol⁻¹ but this value drops to 1.47 emu K mol⁻¹ as the temperature is lowered to 2 K. The X-band EPR spectra for Co₃(mpeptea)₂²⁺ show g values of 2.3 at room temperature. The magnetic behavior is quite different from that in compounds with open Co₃⁶⁺ units. A discussion is provided.     

Assessment of Contaminant Retention in Constructed Wetland Sediments

The A‐01 wetland treatment system (WTS) was designed to remove metals from an industrial effluent at the Savannah River Site, Aiken, SC. Sequential extraction data were used to evaluate remobilization and retention of Cu, Pb, Zn, Mn, and Fe in the wetland sediment. Remobilization of metals was determined by the Potentially Mobile Fraction (PMF) and metal retention by the Recalcitrant Factor (RF). The PMF, which includes water soluble, exchangeable, and amorphous oxides fractions, is the contaminant fraction that has the potential to enter into the mobile aqueous phase under fluctuating environmental conditions. PMF values were low for Cu, Zn, and Pb (13–27 %) and high for Fe and Mn (62–70 %). The RF, which includes crystalline oxides, sulfides or silicates and aluminosilicates, is the ratio of strongly bound fractions to the total concentration of elements in sediment. RF values ranged from 73–87 % for Cu, Zn, and Pb, indicating high retention in the sediment and from 30–38 % for Fe and Mn, indicating low retention. Contaminant retention, which is determined by solid phase metal speciation, determines the potential mobility and bioavailability of captured metals in wetland sediments; hence, their likelihood of being released if chemical, physical, or biological conditions within the wetland change.     

Heterobinuclear copper(II)-nickel(II) complexes of macrocyclic oxamide with diamines and tetraazacyclam as blocking ligands: synthesis, crystal structure and magnetic properties

Three novel oxamido-bridged heterobinuclear copper(II)-nickel(II) complexes derived from macrocylic oxamido compound with diamines and tetraazacyclam as blocking ligands were synthesized and characterized by IR, ESR and electronic spectra. Their formula is [Cu(L)Ni(en)₂](ClO₄)₂·0.5C₂H₅OH·H₂O (1), [Cu(L)Ni(tmd)₂](ClO₄)₂·4H₂O (2) and [Cu(L)Ni(rac-cth)](ClO₄)₂·CH₃OH (3), where L=1,4,8,11-tetraazacyclotradecanne-2,3-dione, en=1,2-diaminoethande, tmd=1,3-diaminopropane and rac-cth is rac-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane. The crystal structures of the three complexes have been determined. The structures consist of binuclear units in which the copper(II) ion is in a square-planar environment and linked to the nickel(II) ion via the exo-cis oxygen atoms of the oxamido macrocyclic ligand, with Cu?Ni separations of 5.311 (1), 5.420 (2) and 5.307 Å (3), respectively. The temperature dependence of the magnetic susceptibility for 1, 2 and 3 was analyzed by means of the Hamiltonian ?=−2J?_Ni?_Cu, leading to J=−52.8, −45.7 and −56.9 cm⁻¹ for 1, 2 and 3, respectively.