Accumulation of heavy metals and arsenic with medicinal herbal raw material of common shovel harvested in Voronezh region

The Voronezh region is traditionally the most important area of crop production and agriculture. The purpose of the research was to study the contamination with heavy metals of medicinal plant raw materials of the Voronezh region using the example of the roots of ordinary burdock, prepared in urbo- and agro-ecosystems, which have various anthropogenic effects on themselves. The accumulation of heavy metals (lead, mercury, cadmium, nickel, copper, zinc, cobalt, chromium) and arsenic in 51 samples of raw materials was studied. By comparing the heavy metal content in the upper soil layers of the region and the content of these elements in the roots of the bladder, it can be assumed that there are significant physiological barriers to the accumulation of ecotoxicants in the roots of the bladder, which is especially noticeable for elements such as lead, mercury, arsenic, cadmium, cobalt and chromium. At the same time, this type of medicinal vegetal raw material is able to selectively concentrate some heavy metals included in the active centers of enzyme systems (copper and zinc). Thus, for an ordinary bladder under conditions of anthropogenic load, an edaphotype is formed, which is as a result of selection in conditions of anthropogenic pollution of the external environment and the manifestation of adaptation to these conditions.

Study of the tectonic structure and modern geodynamics of the nickel-copper-sulfide Kun-Manyo deposit at the stage of its field the development

Currently, the Kun-Manyo nickel-copper-sulfide deposit in the north of the Khabarovsk Krai is being prepared for development, with part of the reserves expected to be mined by underground mining. To justify the rational order of opening and excavation of sub-ore reserves it is necessary to have objective information on rock mass condition, which can be received as a result of complex geodynamic and geomechanical investigations. The established geodynamic position of the deposit, determined by its location at the junction of actively interacting large tectonic elements of the Euro-Asian tectonic plate – the tectonic stress of the North Asian craton and the Amur plate, as well as within the modern Olekmo-Stanovo seismic zone, has allowed the massif of the field area to be classified as tectonically stressed. An analysis of the data of the GPS-observation points on the territory of the Russian part of the Amur tectonic plate, the results of calculations of the vector field of velocities of modern movements of points, made within the framework of the ITRF – 2000 coordinate system, as well as the results of in-situ geomechanical studies of rock massifs of the Amur Plate’s rock-bump hazardous deposits, have made it possible to establish the current tectonic regime of the deposit area – a region of intense modern compression with a predicted intensity of more than 50 MPa. By methods of morphometric analysis and remote sensing, it has been found that the relative relief excesses were significant (700–1000 m), which may lead to an uncompensated horizontal component of geostatic stress. The most extended lineaments of the relief have predominantly southeasterly extension. The identified features of the tectonic structure and regional neotectonics have made it possible to determine the most probable direction and magnitude of the current main horizontal compression, which could be further used in solving various geomechanical problems in the exploitation of the field.

Electrodeposition of nano-Cu, Ni and binary Ni/Cu into nano-porous AAO layer for high-efficiency black spectrally selective coating

Background Anodic aluminum oxide (AAO) template is widespread due to its diverse metal nanostructures. Various solar selective black coatings on aluminum oxide template were investigated. Spectrally selective nano-coating of nickel, copper and nickel–copper on anodized aluminum was produced. Results The coatings were performed via electrodeposition and evaluated by measurement of coating thickness, hardness and optical properties. Also, these coatings were analyzed by scanning electron microscope, energy-dispersive X-ray spectroscopic and polarization studies in 3.5% NaCl solution. The anodized aluminum showed higher corrosion resistance (4.8284 KΩ) and lower corrosion rate (0.02189 mm/year). However, the electro-colored Al with Cu for 60 min showed the highest corrosion rate of 0.1942 mm/y, compared with other Al samples. The effect of anodizing time on the metal density and the optical efficiency of black copper coating was studied. Results The obtained solar panels exhibit low values of solar reflectance within the visible range and high solar absorption efficiency. These coatings are highly efficient and adequate for any solar system.

Compounds of 6, 13-Diamino-6, 13-Dimethyl-1, 4, 8, 11 - Tetraazacyclotetradecane

<p>The reaction of bis-(diaminoethane)nickel(II) chloride, ([Ni(en)2]Cl2 in methanol with formaldehyde and nitroethane in the presence of triethylamine proceeds readily to produce (6, 13-dimethyl-6, 13-dinitro-1, 4, 8, 11-tetraazacyclotetradecane)nickel(II) chloride, [Ni(dini)] - Cl2. Reduction of the nitro groups of this compound by catalytic hydrogenation yields three isomers of the pendant arm macrocyclic complex (6, 13-diamino-6, 13-dimethyl-1, 4, 8, 11-tetraazachyclotetradecane)nickel(II) chloride, designated a-, b- and c-[Ni(diam)]Cl2. These were separated by fractional crystallization. The aisomer was observed to isomerizes slowly in solution to the b- form. A parallel dissociation reaction of the a- isomer was also observed. The demetallation of a- and b- isomers of the diam complex of nickel by reaction with cyanide or concentrated acid at 140 degrees C produces the macrocycle meso-(6, 13-diamino-6, 13-dimethyl-1, 4, 8, 11-tetraazacyclotetra-decane), diam. A variety of hexamine, pentamine and tetramine complexes of diam with nickel(II), copper(II), cobalt(II) and (III), chromium(III), palladium(II), rhodium(III), zinc(II) and cadmium(II) were prepared. Hexamine and tetramine forms of labile metal complexes could be rapidly and reversibly interconverted by altering the pH. The hexamine cobalt(III) cation, [Co(diam)]3+ was by far the most inert of the prepared cobalt(III) complexes, remaining unaffected in hot acidic solutions. In contrast, a single pendant arm of the hexamine [Cr(diam)]3+ cation could be dissociated in acid. (Two possibly triamine complexes of lead were also prepared). These compounds were characterized by elemental analysis, magnetic measurements, electronic, infrared, 1H and 13C nuclear magnetic resonance spectra. The pendant arm protonation constants (log K) of diam and selected complexes of nickel, copper and palladium were calculated from potentiometric titration measurements at 25 degrees C. The log K values for diam at 25 degrees C (I = 0.1 M NaclO4) were 11.15, 9.7, 6.2 and 5.3. Kinetics of the parallel isomerization and dissociation of a-[Ni(dimH2)]4+ in HCl/NaCl solutions were monitored spectrophotometrically at 50 degrees C. The rate of reaction in acidic solutions showed a non-linear dependency on acid concentration. The observed first order rate constant (kobs) for disappearance of a-[Ni(diamH2)]4+ (by isomerization and dissociation) in 2.0 M HCl, 0.1 M NaOH and 2.0 M NaCl were 3.05 x 10-4, 2.0(3) x 10-2 and 5.0 x 10-5 s-1 respectively. The rate of the dissociation component of the reaction of a-[Ni(diamH2)]4+ in 2.0 M HCl at 50 degrees C was 1.82 x 10-7 s-1. Acid bydrolysis kinetics of (Cu[diamH2])(ClO4)4 in hydrochloric acid and perchloric acid at 50 and 70 degrees C were studied spectrophotometrically. The reactions were slow and the observed first order rate constants were to a first approximation independent of the particular acid or its concentration. The observed first order rate constants were 1 x 10-9 and 8 x 10-9 s-1 at 50 and 70 degrees C respectively. Questions about the nature of the reaction being followed have been raised.</p>

Compounds of 6, 13-Diamino-6, 13-Dimethyl-1, 4, 8, 11 - Tetraazacyclotetradecane

<p>The reaction of bis-(diaminoethane)nickel(II) chloride, ([Ni(en)2]Cl2 in methanol with formaldehyde and nitroethane in the presence of triethylamine proceeds readily to produce (6, 13-dimethyl-6, 13-dinitro-1, 4, 8, 11-tetraazacyclotetradecane)nickel(II) chloride, [Ni(dini)] - Cl2. Reduction of the nitro groups of this compound by catalytic hydrogenation yields three isomers of the pendant arm macrocyclic complex (6, 13-diamino-6, 13-dimethyl-1, 4, 8, 11-tetraazachyclotetradecane)nickel(II) chloride, designated a-, b- and c-[Ni(diam)]Cl2. These were separated by fractional crystallization. The aisomer was observed to isomerizes slowly in solution to the b- form. A parallel dissociation reaction of the a- isomer was also observed. The demetallation of a- and b- isomers of the diam complex of nickel by reaction with cyanide or concentrated acid at 140 degrees C produces the macrocycle meso-(6, 13-diamino-6, 13-dimethyl-1, 4, 8, 11-tetraazacyclotetra-decane), diam. A variety of hexamine, pentamine and tetramine complexes of diam with nickel(II), copper(II), cobalt(II) and (III), chromium(III), palladium(II), rhodium(III), zinc(II) and cadmium(II) were prepared. Hexamine and tetramine forms of labile metal complexes could be rapidly and reversibly interconverted by altering the pH. The hexamine cobalt(III) cation, [Co(diam)]3+ was by far the most inert of the prepared cobalt(III) complexes, remaining unaffected in hot acidic solutions. In contrast, a single pendant arm of the hexamine [Cr(diam)]3+ cation could be dissociated in acid. (Two possibly triamine complexes of lead were also prepared). These compounds were characterized by elemental analysis, magnetic measurements, electronic, infrared, 1H and 13C nuclear magnetic resonance spectra. The pendant arm protonation constants (log K) of diam and selected complexes of nickel, copper and palladium were calculated from potentiometric titration measurements at 25 degrees C. The log K values for diam at 25 degrees C (I = 0.1 M NaclO4) were 11.15, 9.7, 6.2 and 5.3. Kinetics of the parallel isomerization and dissociation of a-[Ni(dimH2)]4+ in HCl/NaCl solutions were monitored spectrophotometrically at 50 degrees C. The rate of reaction in acidic solutions showed a non-linear dependency on acid concentration. The observed first order rate constant (kobs) for disappearance of a-[Ni(diamH2)]4+ (by isomerization and dissociation) in 2.0 M HCl, 0.1 M NaOH and 2.0 M NaCl were 3.05 x 10-4, 2.0(3) x 10-2 and 5.0 x 10-5 s-1 respectively. The rate of the dissociation component of the reaction of a-[Ni(diamH2)]4+ in 2.0 M HCl at 50 degrees C was 1.82 x 10-7 s-1. Acid bydrolysis kinetics of (Cu[diamH2])(ClO4)4 in hydrochloric acid and perchloric acid at 50 and 70 degrees C were studied spectrophotometrically. The reactions were slow and the observed first order rate constants were to a first approximation independent of the particular acid or its concentration. The observed first order rate constants were 1 x 10-9 and 8 x 10-9 s-1 at 50 and 70 degrees C respectively. Questions about the nature of the reaction being followed have been raised.</p>

Some Biogeochemical Characteristics of the Trace Element Bioaccumulation in the Benthic Fauna of the Piip Volcano (The Southwestern Bering Sea)

The Piip Volcano is a submarine volcanic edifice occupying the central part of the Volcanologists Massif in the southwestern Bering Sea, with two tops, southern and northern. The minimum depth of the northern top is located at 368 m, and of the southern at 464 m. Active hydrothermal venting occurring at both summits of the volcano supports diverse biological communities, including animals specific for chemosynthetic habitats. In benthic organisms inhabiting the northern and southern tops of the Piip Volcano, for the first time, we examined distribution patterns of the following trace elements: titanium, vanadium, chromium, manganese, iron, nickel, copper, zinc, arsenic, selenium, zirconium, molybdenum, silver, cadmium, antimony, barium, tungsten, lead, bismuth, and uranium. The element contents were quantified by the ICP-MS. Total carbon (TC) and total inorganic carbon (TIC) were determined using a Shimadzu TOC-L-CPN and mineral composition of sediment was determined using the XRD. In the water of the biotope from the northern top, concentrations of Mn, Zn, Ag, Cd, Sb, W, Pb were 2–6 times, and Ba was 50 times higher than those from the southern top. This was attributed to the lower temperature of fluids emanating at the southern top. An abundant population of Calyptogena pacifica (Bivalvia: Vesicomyidae: Pliocardiinae) was found only at the southern top. The main target of most trace elements, such as Fe, V, Cr, Co, Ni, Zn, As, Mo, Ag, Cd, W, Pb, Bi, and U were the soft parts of Calyptogena pacifica (with high TOC content, on average 53.1% in gills and 49.6% in the rest of the body). Gills were characterized by particular high contents (>100 µg g-1 dry w.) of Zn, Cd, Fe, Ni, Cu, and Pb, which can form sulphides or be associated with them. Shells of C. pacifica, as well as Brachiopoda, were depleted in these elements, as well as tissues of the carnivores Paguridae (Crustacea) and Actiniaria (Anthozoa). In suspension feeders from both tops, the lower contents of most elements were detected. Estimation of Biological Concentration Factor (BCF) for most elements varied from 102 to 104, reaching n105 for Ni, Zn, Ag, Ca, and Pb. A significant difference in BCF values between Fe and Mn was revealed.

Compounds of 6, 13-Diamino-6, 13-Dimethyl-1, 4, 8, 11 - Tetraazacyclotetradecane

<p>The reaction of bis-(diaminoethane)nickel(II) chloride, ([Ni(en)2]Cl2 in methanol with formaldehyde and nitroethane in the presence of triethylamine proceeds readily to produce (6, 13-dimethyl-6, 13-dinitro-1, 4, 8, 11-tetraazacyclotetradecane)nickel(II) chloride, [Ni(dini)] - Cl2. Reduction of the nitro groups of this compound by catalytic hydrogenation yields three isomers of the pendant arm macrocyclic complex (6, 13-diamino-6, 13-dimethyl-1, 4, 8, 11-tetraazachyclotetradecane)nickel(II) chloride, designated a-, b- and c-[Ni(diam)]Cl2. These were separated by fractional crystallization. The aisomer was observed to isomerizes slowly in solution to the b- form. A parallel dissociation reaction of the a- isomer was also observed. The demetallation of a- and b- isomers of the diam complex of nickel by reaction with cyanide or concentrated acid at 140 degrees C produces the macrocycle meso-(6, 13-diamino-6, 13-dimethyl-1, 4, 8, 11-tetraazacyclotetra-decane), diam. A variety of hexamine, pentamine and tetramine complexes of diam with nickel(II), copper(II), cobalt(II) and (III), chromium(III), palladium(II), rhodium(III), zinc(II) and cadmium(II) were prepared. Hexamine and tetramine forms of labile metal complexes could be rapidly and reversibly interconverted by altering the pH. The hexamine cobalt(III) cation, [Co(diam)]3+ was by far the most inert of the prepared cobalt(III) complexes, remaining unaffected in hot acidic solutions. In contrast, a single pendant arm of the hexamine [Cr(diam)]3+ cation could be dissociated in acid. (Two possibly triamine complexes of lead were also prepared). These compounds were characterized by elemental analysis, magnetic measurements, electronic, infrared, 1H and 13C nuclear magnetic resonance spectra. The pendant arm protonation constants (log K) of diam and selected complexes of nickel, copper and palladium were calculated from potentiometric titration measurements at 25 degrees C. The log K values for diam at 25 degrees C (I = 0.1 M NaclO4) were 11.15, 9.7, 6.2 and 5.3. Kinetics of the parallel isomerization and dissociation of a-[Ni(dimH2)]4+ in HCl/NaCl solutions were monitored spectrophotometrically at 50 degrees C. The rate of reaction in acidic solutions showed a non-linear dependency on acid concentration. The observed first order rate constant (kobs) for disappearance of a-[Ni(diamH2)]4+ (by isomerization and dissociation) in 2.0 M HCl, 0.1 M NaOH and 2.0 M NaCl were 3.05 x 10-4, 2.0(3) x 10-2 and 5.0 x 10-5 s-1 respectively. The rate of the dissociation component of the reaction of a-[Ni(diamH2)]4+ in 2.0 M HCl at 50 degrees C was 1.82 x 10-7 s-1. Acid bydrolysis kinetics of (Cu[diamH2])(ClO4)4 in hydrochloric acid and perchloric acid at 50 and 70 degrees C were studied spectrophotometrically. The reactions were slow and the observed first order rate constants were to a first approximation independent of the particular acid or its concentration. The observed first order rate constants were 1 x 10-9 and 8 x 10-9 s-1 at 50 and 70 degrees C respectively. Questions about the nature of the reaction being followed have been raised.</p>

Compounds of 6, 13-Diamino-6, 13-Dimethyl-1, 4, 8, 11 - Tetraazacyclotetradecane

<p>The reaction of bis-(diaminoethane)nickel(II) chloride, ([Ni(en)2]Cl2 in methanol with formaldehyde and nitroethane in the presence of triethylamine proceeds readily to produce (6, 13-dimethyl-6, 13-dinitro-1, 4, 8, 11-tetraazacyclotetradecane)nickel(II) chloride, [Ni(dini)] - Cl2. Reduction of the nitro groups of this compound by catalytic hydrogenation yields three isomers of the pendant arm macrocyclic complex (6, 13-diamino-6, 13-dimethyl-1, 4, 8, 11-tetraazachyclotetradecane)nickel(II) chloride, designated a-, b- and c-[Ni(diam)]Cl2. These were separated by fractional crystallization. The aisomer was observed to isomerizes slowly in solution to the b- form. A parallel dissociation reaction of the a- isomer was also observed. The demetallation of a- and b- isomers of the diam complex of nickel by reaction with cyanide or concentrated acid at 140 degrees C produces the macrocycle meso-(6, 13-diamino-6, 13-dimethyl-1, 4, 8, 11-tetraazacyclotetra-decane), diam. A variety of hexamine, pentamine and tetramine complexes of diam with nickel(II), copper(II), cobalt(II) and (III), chromium(III), palladium(II), rhodium(III), zinc(II) and cadmium(II) were prepared. Hexamine and tetramine forms of labile metal complexes could be rapidly and reversibly interconverted by altering the pH. The hexamine cobalt(III) cation, [Co(diam)]3+ was by far the most inert of the prepared cobalt(III) complexes, remaining unaffected in hot acidic solutions. In contrast, a single pendant arm of the hexamine [Cr(diam)]3+ cation could be dissociated in acid. (Two possibly triamine complexes of lead were also prepared). These compounds were characterized by elemental analysis, magnetic measurements, electronic, infrared, 1H and 13C nuclear magnetic resonance spectra. The pendant arm protonation constants (log K) of diam and selected complexes of nickel, copper and palladium were calculated from potentiometric titration measurements at 25 degrees C. The log K values for diam at 25 degrees C (I = 0.1 M NaclO4) were 11.15, 9.7, 6.2 and 5.3. Kinetics of the parallel isomerization and dissociation of a-[Ni(dimH2)]4+ in HCl/NaCl solutions were monitored spectrophotometrically at 50 degrees C. The rate of reaction in acidic solutions showed a non-linear dependency on acid concentration. The observed first order rate constant (kobs) for disappearance of a-[Ni(diamH2)]4+ (by isomerization and dissociation) in 2.0 M HCl, 0.1 M NaOH and 2.0 M NaCl were 3.05 x 10-4, 2.0(3) x 10-2 and 5.0 x 10-5 s-1 respectively. The rate of the dissociation component of the reaction of a-[Ni(diamH2)]4+ in 2.0 M HCl at 50 degrees C was 1.82 x 10-7 s-1. Acid bydrolysis kinetics of (Cu[diamH2])(ClO4)4 in hydrochloric acid and perchloric acid at 50 and 70 degrees C were studied spectrophotometrically. The reactions were slow and the observed first order rate constants were to a first approximation independent of the particular acid or its concentration. The observed first order rate constants were 1 x 10-9 and 8 x 10-9 s-1 at 50 and 70 degrees C respectively. Questions about the nature of the reaction being followed have been raised.</p>