Influence of Polyphenols and Quinones on Aquatic Plants and Their Blocking of SH-Groups

The influence of dioxybenzenes and their quinones on Dunaliella salina, Nitella sp. and Elodea canadensis was investigated. It was established that the higher the rate of polyphenol oxidation by the aqueous plants, the higher the toxicity of the compound being studied is and the larger the reduction of the SH-group content due to the incubation of plants in these polyphenol solutions is. Formation of o- and p-benzoquinones by the aquatic plants in the course of dioxybenzene oxidation was proved. Treatment of plants with quinone solutions led to a larger SH-group concentration drop than with phenols. Oxidation products of pyrocatechol, caffeic and chlorogenic acids caused the greatest decrease of the SH-group content directly at the moment of their preparation, i. e., when the o-quinone concentration was at its maximum. The conclusion is drawn that a higher degree of toxicity to the aquatic plants of pyrocatechol and hydroquinone, in comparison with other phenols, is due to their ability to oxidize phenols to quinones. It is suggested that one of the possible biochemical mechanisms for demonstrating the toxic action of the phenol oxidation products is the blocking of SH-groups.     

Methods of Analyzing Quinones in Water and Their Application in Studying the Effects of Hydrophytes on Phenols. Part 5: Elimination of Carcinogenic Amines from Solutions under the Action of Nitella

Under laboratory conditions and conditions similar to practice in the shore region of the lake Baikal, Nitella was added to aqueous solutions of benzidine and α-naphthylamine in the concentration range of 10^?3 … 10^?4 M. The results are summarized graphically in in tables. The two substances were accumulated in the protoplasm of the Nitella cells in considerable quantities.     

Methods of Analyzing Quinones in Water and Their Application in Studying the Effects of Hydrophytes on Phenols. Part 4: Accumulation of Exogenic Phenols,Localization of Endogenic Phenols and o-Diphenol Oxidase in Nitella Cells

By using Nitella, with the aid of a technique which is described in detail the uptake of resorcinol by the cytoplasm was demonstrated and quantitatively determined under different test conditions. In contrast to the phenol oxidation products of hydroquinone and pyrocatechol, the further “fate” of the resorcinol taken up by the cell substance is not yet fully clear. The rate of resorcinol absorption has been defined with a permeability constant.     

Cooxidation of Carcinogenic Benzo(a) Pyrene and Phenols by Horseradish Peroxidase (Armoracia lapathifolia)

The catalytic activity of horseradish (Armoracia lapathifolia) peroxidase in the oxidation reactions of benzo(a)pyrene (BP) and phenols, separately and in admixture, has been studied. Experiments were carried out with model phenols from industrial sewage (phenol, m-, p-cresols, catechol, hydroquinone, resorcinol, orcinol), keeping to the real concentration ratio of reagents, 0.5 mM for phenols, 0.1 nM for benzo(a)pyrene. The total oxidation process for all reagents tested is described by the second-order formal kinetic equation up to 60 … 90% of their conversion. Addition of peroxidase increases the rate of oxidation of benzo(a)pyrene and phenols 2 … 6 times as compared with the control test (with hydrogen peroxide), whereas a linear dependence of the rate of benzo(a)pyrene oxidation on the enzyme concentration is observed. By cooxidation a mutual inhibition of benzo(a)pyrene and phenols is established whose degree depends on the phenol-chemical structure and varies in the range of 23 … 58% for BP under the influence of phenols and 35 … 80% for phenols under the influence of benzo(a)pyrene. The results obtained permit a supposition that peroxidase containing plants are capable of simultaneously transforming carcinogenic benzo(a)pyrene and toxic phenols in water reservoirs and in the soil, thus promoting the detoxication of environment.     

Biodegradation of Petroleum Hydrocarbons by Pseudomonas putida Strain MHF 7109

Pseudomonas putida MHF 7109 has been isolated and identified from cow dung microbial consortium for biodegradation of selected petroleum hydrocarbon compounds – benzene, toluene, and o‐xylene (BTX). Each compound was applied separately at concentrations of 50, 100, 250, and 500 mg L^?1 in minimal salt medium to evaluate degradation activity of the identified microbial strain. The results indicated that the strain used has high potential to degrade BTX at a concentration of 50 mg L^?1 within a period of 48, 96, and 168 h, respectively; whereas the concentration of 100 mg L^?1 of benzene and toluene was found to be completely degraded within 120 and 168 h, respectively. Sixty‐two percent of o‐xylene were degraded within 168 h at the 100 mg L^?1 concentration level. The maximum degradation rates for BTX were 1.35, 1.04, and 0.51 mg L^?1 h^?1, respectively. At higher concentrations (250 and 500 mg L^?1) BTX inhibited the activity of microorganisms. The mass spectrometry analysis identified the intermediates as catechol, 2‐hydroxymuconic semialdehyde, 3‐methylcatechol, cis‐2‐hydroxypenta‐2,4‐dienoate, 2‐methylbenzyl alcohol, and 1,2‐dihydroxy‐6‐methylcyclohexa‐3,5‐dienecarboxylate, for BTX, respectively. P. putida MHF 7109 has been found to have high potential for biodegradation of volatile petroleum hydrocarbons.     

Extraction of Phenol and Chlorophenols Using Ionic Liquid [Bmim]+[BF4]− Dissolved in Tributyl Phosphate

In the present work, experiments have been carried out with a focus to reduce the volume requirement of solvent by mixing with imidazolium based ionic liquids (ILs) for the solvent extraction of phenol, p‐chlorophenol, 2,4‐dichlorophenol, 2,4,6‐trichlorophenol, and pentachlorophenol from aqueous solutions. The effect of aqueous phase pH (2–12), agitation speed (100–450 rpm), solute concentration in feed (2–50 mg/L), temperature (303–333 K), treat ratio (1–11), and 1‐butyl‐3‐methyl imidazolium tetrafluoroborate [Bmim]⁺[BF₄]^? volume in tributyl phosphate (TBP; 0–0.7% v/v) on extraction of phenols has been studied and optimized. Parameters like strip phase pH (3–13) and stripping agent concentration (0.001–0.009 N) have also been studied for stripping of phenols from solvent phase. It has been found that 0.5% v/v of ionic liquid [Bmim]⁺[BF₄]^? in solvent TBP extracts more than 97.5% of phenol and chlorophenols from aqueous solutions with a treat ratio (aqueous to solvent phase ratio) of 5. Transport mechanism for extraction and stripping of phenol and chlorophenols using ionic liquid [Bmim]⁺[BF₄]^? has been discussed. The results show that by appropriate selection of extraction and stripping conditions, it is possible to remove nearly all phenols with a treat ratio of 5.     

Use of Thin-Layer and Paper Chromatography for Detection of Ortho- and Para-Quinones Formed in the Course of Phenol Oxidation

In order to detect the labiles in the aqueous solution of the benzene- and naphthoquinones, they were preliminarily transformed with the aid of the benzene sulphinic acid into stable sulphonic derivatives. Methods were developed of the chromatographic detection on paper and in a thin layer of the β-naphthol, phenol, ortho-, para-dioxybenzenes and their sulphonic derivatives with joint presence in the solution of ortho- and para-isomers of the dioxyderivatives. For the chromatographic separation of the ortho- and para-derivatives, the ability of ortho-isomers to form chelate complexes with boric acid or to precipitate with mean laed acetate salt was made use of. With the aid of the given method, the stage of the quinone formation in the course of abiogenic and biochemical (under the action of Nitella sp.) oxidation of benzene, phenol, β-naphthol, pyrocatechol, hydroquinone has been proved. Oxidation under the action of Nitella sp. leads to the formation of the dioxybenzene ortho-isomers and their derivatives.     

The Accumulation of Crimidin in Some Fish Organs

The accumulation of crimidin in total samples and in some organs of five fish species was studied under experimental conditions. The species were Cyprinus carpio, Carassius carassius, Tinca tinca, Scardinus erythrophthalmus and Leucaspius delineatus. Fish were exposed to concentrations of 10 mg · l^?l and 50 mg · l^?1. During short-term experiments water and fish samples were taken at intervals of t = 0, 6, 12, 24, 48 and 72 hours, during the long-term experiment sampling was performed weekly for six weeks. Total samples were analysed for C. carassius, T. tinca, S. erythrophthalmus and L. delineatus. Samples of individual organs and tissues were taken as follows: C. carpio – gills, digestive tract, muscular tissue, kidneys, gonads; C. carassius – gills, digestive tract, muscular tissue, ovaries, testes. Crimidin was determined by gas chromatography. In samples from the short-term experiments at a concentration of 10 mg · l^?1 in the water the amount was roughly 10¹–10 mg · kg^?1, at a concentration of 50 mg · l^?1 in the water roughly 10¹ mg · kg^?1. In most cases the accumulation coefficient was lower than 1.0. The accumulation capacity of individual fish species did not differ greatly. Of the internal organs only the kidneys had a high accumulation capacity, otherwise the highest values were found in muscular tissue and the gills. After one – three weeks the amount of crimidin in most organs falls, and after transfer to clean water there is a general sharp decline. Thus crimidin is not firmly bound in the body.     

Oxidation of Benzo(a) Pyrene Catalyzed by Phenol Oxidases of Alga Nitella sp. and Potato Tubers

The kinetics of oxidation of carcinogenic benzo(a)pyrene (0.1 nM solution in phosphate buffer) catalyzed by enzyme protein of soil and water plants (potato tubers and alga Nitella sp.) has been studied. The benzo(a)pyrene oxidation rate is determined by the phenoloxidase activity of the enzyme protein from both sources to an equal degree and expressed by the Michaelis-Menten equation. The values for k_cat and apparent K_m were (0.97 ± 0.14) Ms^?1 and 33 ± 6 μM, respectively. The presence of other compounds (including protein substances) in acetone preparations of potato tubers considerably suppresses its catalytic activity in relation to benzo(a)pyrene. Consequently, in the polluted biosphere some water plants, such as alga Nitella sp., and potato tuber can transform carcinogenic benzo(a)pyrene (BP). As oxidation products, all three BP-quinones, i.e. 1,6-, 3,6-and 6,12-diones, were identified.     

Methods of Analyzing Qninones in Water and Their Application in Studying the Effects of Hydrophytes on Phenols. Part 1: Quinone Determination with Benzene Sulfinic Acid

By the example of some phenols and qninones, in aqueous solutions possibilities for the quantitative determination are tested separately and in the mixture. Methods for thin-layer chromatography and spectrophotometry were developed. There can be chromatographically deteeted between 5 and 80 μg of substance. Phenol and quinone concentrations of 1.5 · 10^?3 … 0.5 · 10^?4 M were spectrophotometrically investigated.     

Impairments Induced by Sublethal Doses of Sevin and Thiodan on the Brain of a Freshwater Teleost Channa striatus BL. (Channidae)

Prolonged exposure to two pesticides Sevin and Thiodan for 30 days produced impairments in the brain of Channa striatus on the following ways:

• – Separation and damage to meninges of cerebral hemispheres
• – severe damage to all the five layers of the optic textum
• – severe damage to torus longitudinalis
• – partial damage to the molecular and grannular layers of the corpus cerebelli.
• – no effect on diencephalon and myelencephalon.

     

Changes in Water Hydrochemistry in Bays of the Bratsk Reservoir Caused by Forest Harvesting Operations

For the first time, the results of studying the hydrochemical characteristics of bays in the Bratsk Reservoir, subject to the effect of forest harvesting operations are given. The obtained data include the concentrations of NO₃^?, NO₂^?, NH₄⁺, PO₄^-3, SiO₂, phenols, oil products, and organic matter and the oxygen regime of water in the bays. The concentration and distribution in water of biogenic elements and O₂-typical of wood decay processes-demonstrate the high self-purification capacity of ecosystems in the majority of bays. At the same time, water of some bays shows signs of eutrophication and high concentrations of phenols and oil products.     

Bioreduction of Hexavalent Chromium by Live and Active Phanerochaete chrysosporium: Kinetics and Modeling

In this work the potential of live and active Phanerochaete chryosporium, a white rot fungi, to remove lower Cr(VI) concentration from aqueous solutions was reported for the first time. A medium pH had significant effect on the growth of the fungus and bioremoval of Cr(VI). Substrate inhibition on the growth of Phanerochaete chrysosporium was evident beyond 20 g L^?1 of dextrose concentration. A maximum biomass concentration of 15.64 g L^?1 was obtained for an initial dextrose concentration of 20 g L^?1 in metal free medium at pH 6.0. An increase in Cr(VI) concentration beyond 10 mg L^?1 inhibited the growth of the fungi, thereby, reducing the chromium bioremoval efficiency. A maximum reduction efficiency of 98.92% was reported for an initial metal concentration of 10 mg L^?1. A mathematical expression for the bioreduction of Cr(VI) considering the organic compounds in the cells was proposed.     

Zinc Induced Changes in the Nucleic Acids and Protein Metabolism in the Fingerlings of a Freshwater Murrel,Channa punctatus

Fingerlings of Channa punctatus, a freshwater murrel, when subjected to a sublethal concentration of 12 mg l^?1 zinc for 20 days elicited a significantly decreased (P<0.01) RNA content and hypoproteinemia in their liver. However, an exposure for 10 days under the same condition did not produce a significant alternation (P>0.05) neither in the nucleic acids (RNA – DNA) nor in the protein content. Results are discussed in relation to the pollutional stress of this heavy metal.     

Studies on the Toxicity of a few Pesticides on Colisa fasciatus and Notopterus notopterus with Reference to Histopathology and Histochemistry. Part 1: Bioassay Studies

An attempt has been made to study the toxicity of two commonly used pesticides aldrin (organochlorine) and ethyl-parathion (organophosphorus) to the fish Colisa fasciatus (Anabantidae) and Notopterus notopterus (Notopteridae). During bioassay studies, the behaviour of the fishes was recorded. The aldrin concentration used lies between 0.021 mg/1 and 0.042 mg/1 for C. fasciatus and 0.00056 mg/1 and 0.00135 mg/1 for N. notopterus. The ethyl-parathion concentration used lies between 1.8 mg/1 and 3.7 mg/1 for C. fasciatus and 0.49 mg/1 and 1.00 mg/1 for N. notopterus.

• – The effect of lethal aqueous concentrations of pesticides on the Fishes prior to death are usually manifested by excitation, erratic swimming ability, difficulty in respiration, increasing in ventilation rate, jerky movements of body and fin fast, up- and downward movements, convulsions, loss of equilibrium, loss of the original colour of the body skin and the excess secretion of mucus by the gills and the body wall.
• – the TL_m values for 24, 48 and 96 hours of exposition are determined for both species of fish and both pesticides at the following variables:

• ? three levels of temperature,
• ? three levels of dissolved oxygen,
• ? three levels of pH,
• ? three fish sizes.

• – statistical analysis of variance shows, that all variables have a significant effect on the TL_m values of both pesticides for both fish species;
• – Aldrin (chlorinated hydrocarbon) is more toxic than ethylparathion (organophosphate) at all variables;
• – Colisa fasciatus is the more resistant species than Notopterus notopterus.
• – the relationship between the total number of the fishes N₀, survival numbers N and time t can be expressed by a mathematical formula as:
• – the harmless concentration to C. fasciatus ranged from 0.0049 mg/1 to 0.0161 for aldrin, 0.54 mg/1 to 0.99 mg/1 for ethyl-parathion and to N. notopterus from 0.00012 mg/1 to 0.00045 mg/1 for aldrin, 0.10 mg/1 to 0.21 mg/1 for ethyl-parathion;
• – the aldrin should be diluted at least 4000 times and ethyl-parathion 320 times of its actual concentration.

     

Inhibition Concentration of Phenolic Substances under Different Cultivation Conditions. Part II: Impact of Dissolved Oxygen Concentration and Temperature on Degradation Kinetics

The degradation behaviour of a phenolic waste-water from coking containing easily utilizable carbon sources (volatile fatty acids), substances with toxic effects (phenols and phenolic compounds), and non-biodegradable organic substances (humic-like substances) by an adapted activated sludge is investigated depending on dissolved oxygen concentration (DO) and temperature. In addition, the degradation of an acetate model water with the same population was investigated. The investigations were carried out in a special respiration fermenter system by recording oxygen consumption in DO-static experiments. The oxygen consumption curves were subjected to linear regression analysis, and the maximum oxygen consumption rates were used for further calculations. Evaluation of the degradation kinetics was carried out with non-linear regression analysis via commercial software utilizing the Marquardt-Levenberg algorithm and which tested various kinetic models to obtain the best curve fit. It is shown that the dependence of growth on DO in acetate model water is well represented by Monod kinetics but by contrast can only be described in phenolic wastewater with acceptable goodness by Hill kinetics, modified by a maintenance term. The kinetic constants calculated for the mesophilic range (37 °C) are for the model water as follows: maximum specific growth rate = 0.218 h^?1, half saturation constant with respect to oxygen = 0.297 g L^?1, and for the waste-water: maximum specific growth rate = 0.387 h^?1, half saturation constant with respect to oxygen = 0.013 gL^?1 and maintenance coefficient for oxygen = 0.107 g g^?1 h^?1. For the thermophilic range (55 °C), a higher growth rate but a significant lower yield coefficient are to be observed. The kinetic constants calculated are: maximum specific growth rate = 0.8 h^?1, half saturation constant with respect to oxygen = 0.14 gL^?1 and maintenance coefficient for oxygen = 0.3 g g^?1 h^?1. Therefore, it can be concluded that the toxic effect of the biodegradable phenols causes a maintenance metabolism which leads to higher oxygen demand. The diminution of the limiting DO and the increased maintenance metabolism confirm the assumption that a higher maintenance metabolism leads to increased sensitivity with respect to the cosubstrate oxygen. It can be concluded that the experimental and mathematical methods used permit the maintenance metabolism with respect to oxygen caused by toxic substrates and milieu influences to be accurately determined.     

A Preliminary Study of Chromophoric Dissolved Organic Matter (CDOM) in Lake Taihu,a Shallow Subtropical Lake in China

The optical properties and spatial distribution of chromophoric dissolved organic matter (CDOM) in Meiliang Bay of Lake Taihu were evaluated and compared to the results in literature. Concentrations of dissolved organic carbon (DOC) ranged from 8.75 to 20.19 mg L^?1 with an average of (13.10 ± 3.51) mg L^?1. CDOM absorption coefficients a(λ) at 280 nm, 355 nm, and 440 nm were in the range 11.28...33.46 m^?1 (average (20.95 ± 5.52) m^?1), 2.42...7.90 m^?1 (average (4.92 ± 1.29) m^?1), and 0.65...2.44 m^?1 (average (1.46 ± 0.44) m^?1), respectively. In general, CDOM absorption coefficient and DOC concentration were found to decrease away from the river inflow to Meiliang Bay towards the lake center. The values of the DOC‐specific absorption coefficients a*(λ), given as absorption coefficient related to mass concentration of organic carbon (C) ranged from 0.28 to 0.47 L mg^?1 m^?1 at 355 nm. The determination coefficients between CDOM absorption and DOC concentration decreased with the increase of wavelength from 280 to 550 nm. The linear regression relationship between CDOM absorption at 280 nm and DOC concentration was following: a(280 nm) = 1.507 L mg^?1 m^?1 · DOC + 1.215 m^?1. The spectral slope S values were dependent on the wavelength range used in the regression. The estimated S values decreased with increasing wavelength range used. A significant negative linear relationship was found between CDOM absorption coefficients, DOC‐specific absorption coefficients and estimated S values especially in longer wavelength range. The linear regression relationship between DOC‐specific absorption coefficients at 440 nm and estimated S values during the wavelength range from 280 to 500 nm was following: a*(440 nm) = (–0.021 μm · S + 0.424) L mg^?1 m^?1.     

Zur Konzentrationsabhängigkeit der Sorption von Co(II) an Titanschwamm

The sorption of Co(II) from aqueous solutions on granulated titanium dioxide was investigated in dependence on pH-value (pH = 6 … 10) and solution concentration (c_L = 10^?7 … 10^?2 mol/kg) at 83 °C. The precipitation in the solution occurred at high pH-values and solution concentrations was determined by control experiments without the adsorber. The adsorption isotherms are S-shaped. This can be interpreted as transition from chemisorption at the basic material to surface precipitation.     

The Seashell Wastes as Biosorbent for Reactive Dye Removal from Textile Effluents

This study investigates structural and adsorption properties of the powdered waste shells of Rapana gastropod and their use as a new cheap adsorbent to remove reactive dye Brilliant Red HE‐3B from aqueous solutions under batch conditions. For the powder shells characterization, solubility tests in acidic solutions and X‐ray diffraction (XRD), scanning electron microscopy (SEM), energy‐dispersive X‐ray spectroscopy (EDX), Fourier transform IR spectroscopy (FT‐IR) and thermogravimetric analyses were performed. The results revealed that the adsorbent surface is heterogeneous consisting mainly from calcium carbonate layers (either calcite or aragonite) and a small amount of organic macromolecules (proteins and polysaccharides). The dye adsorptive potential of gastropod shells powder was evaluated as function of initial solution pH (1–5), adsorbent dose (6–40 g L^?1), dye concentration (50–300 mg L^?1), temperature (5–60°C), and contact time (0–24 h). It was observed that the maximum values of dye percentage removal were obtained at the initial pH of solution 1.2, shells dose of 40 g L^?1, dye initial concentration of 50–50 mg L^?1 and higher temperatures; the equilibrium time decreases with increasing of dye concentration. It is proved that the waste seashell powder can be used as low cost bioinorganic adsorbent for dyes removal from textile wastewaters.     

Inhibition Concentration of Phenolic Substances under Different Cultivation Conditions. Part I: Phenol Oxidation by Mixed Microbial Population in a Model System

The effects of oxygen supply rate and the presence or absence of nutrients on the kinetics of phenol degradation and oxygen consumption by a mixed microbial population were tested in a model system. The values for the maximum specific rate of phenol degradation (q_Smax), the saturation constant (K_S), and the inhibition concentration (S_CR) were determined for unlimited growth (K_La = 340 h^?1, growth medium) with 1.7 mmol g^?1 h^?1, 65 mg L^?1, and 190 mg L^?1. Under limitation conditions, alterations occur depending on the type of limitation. Nutrient limitations lead to values of 0.8 mmol g^?1 h^?1, 45 mg L^?1, and 160 mg L^?1, and oxygen limitations lead to 1.2 mmol g^?1 h^?1. 30 mg L^?1, and 120 mg L^?1, respectively. The results suggest that with excess oxygen, the rate of phenol degradation was higher and the inhibition effect of phenol was suppressed to some extent. Under the same high oxygen supply rate, the presence of nutrients in the model water significantly supported the phenol degradation rate.