Electro-oxidation of the dye azure B: kinetics,mechanism, and by-products

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals (^?OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by ^?OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19?×?10⁹ M^?1 s^?1. It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.     

Effects of light and temperature fluctuations on the growth of Myriophyllum spicatum in toxicity tests—a model-based analysis

Laboratory toxicity tests are a key component of the aquatic risk assessments of chemicals. Toxicity tests with Myriophyllum spicatum are conducted based on working procedures that provide detailed instructions on how to set up the experiment, e.g., which experimental design is necessary to get reproducible and thus comparable results. Approved working procedures are established by analyzing numerous toxicity tests to find a compromise between practical reasons (e.g., acceptable ranges of ambient conditions as they cannot be kept completely constant) and the ability for detecting growth alterations. However, the benefit of each step of a working procedure, e.g., the random repositioning of test beakers, cannot be exactly quantified, although this information might be useful to evaluate working procedures. In this paper, a growth model of M. spicatum was developed and used to assess the impact of temperature and light fluctuations within the standardized setup. It was analyzed how important it is to randomly reassign the location of each plant during laboratory tests to keep differences between the relative growth rates of individual plants low. Moreover, two examples are presented on how modeling can give insight into toxicity testing. Results showed that randomly repositioning of individual plants during an experiment can compensate for fluctuations of light and temperature. A method is presented on how models can be used to improve experimental designs and to quantify their benefits by predicting growth responses.     

Coagulant recovery from water treatment plant sludge and reuse in post-treatment of UASB reactor effluent treating municipal wastewater

In the present study, feasibility of recovering the coagulant from water treatment plant sludge with sulphuric acid and reusing it in post-treatment of upflow anaerobic sludge blanket (UASB) reactor effluent treating municipal wastewater were studied. The optimum conditions for coagulant recovery from water treatment plant sludge were investigated using response surface methodology (RSM). Sludge obtained from plants that use polyaluminium chloride (PACl) and alum coagulant was utilised for the study. Effect of three variables, pH, solid content and mixing time was studied using a Box–Behnken statistical experimental design. RSM model was developed based on the experimental aluminium recovery, and the response plots were developed. Results of the study showed significant effects of all the three variables and their interactions in the recovery process. The optimum aluminium recovery of 73.26 and 62.73 % from PACl sludge and alum sludge, respectively, was obtained at pH of 2.0, solid content of 0.5 % and mixing time of 30 min. The recovered coagulant solution had elevated concentrations of certain metals and chemical oxygen demand (COD) which raised concern about its reuse potential in water treatment. Hence, the coagulant recovered from PACl sludge was reused as coagulant for post-treatment of UASB reactor effluent treating municipal wastewater. The recovered coagulant gave 71 % COD, 80 % turbidity, 89 % phosphate, 77 % suspended solids and 99.5 % total coliform removal at 25 mg Al/L. Fresh PACl also gave similar performance but at higher dose of 40 mg Al/L. The results suggest that coagulant can be recovered from water treatment plant sludge and can be used to treat UASB reactor effluent treating municipal wastewater which can reduce the consumption of fresh coagulant in wastewater treatment.     

Determination of specific gravity of municipal solid waste

This investigation was conducted to evaluate experimental determination of specific gravity (G_s) of municipal solid waste (MSW). Water pycnometry, typically used for testing soils was adapted for testing MSW using a large flask with 2000 mL capacity and specimens with 100–350 g masses. Tests were conducted on manufactured waste samples prepared using US waste constituent components; fresh wastes obtained prior and subsequent to compaction at an MSW landfill; and wastes obtained from various depths at the same landfill. Factors that influence specific gravity were investigated including waste particle size, compaction, and combined decomposition and stress history. The measured average specific gravities were 1.377 and 1.530 for as-prepared/uncompacted and compacted manufactured wastes, respectively; 1.072 and 1.258 for uncompacted and compacted fresh wastes, respectively; and 2.201 for old wastes. The average organic content and degree of decomposition were 77.2% and 0%, respectively for fresh wastes and 22.8% and 88.3%, respectively for old wastes. The G_s increased with decreasing particle size, compaction, and increasing waste age. For fresh wastes, reductions in particle size and compaction caused occluded intraparticle pores to be exposed and waste particles to be deformed resulting in increases in specific gravity. For old wastes, the high G_s resulted from loss of biodegradable components that have low G_s as well as potential access to previously occluded pores and deformation of particles due to both degradation processes and applied mechanical stresses. The G_s was correlated to the degree of decomposition with a linear relationship. Unlike soils, the G_s for MSW was not unique, but varied in a landfill environment due both to physical/mechanical processes and biochemical processes. Specific gravity testing is recommended to be conducted not only using representative waste composition, but also using representative compaction, stress, and degradation states.     

A two-generational reproductive toxicity study of zinc in rats

A two-generation reproductive toxicity study of zinc chloride (ZnCl₂) was conducted in rats. F_o male and female rats were administered 0.00 (control), 7.50 (low), 15.00 (mid) and 30.00 (high) mg/kg/day of ZnCl₂. Selected F₁ male and female rats were exposed to the same doses received by their parents (F_o). Exposure of F₀ parental rats to ZnCl₂ showed significant reduction in fertility, viability (days 0 and 4), and the body weight of F₁ pups from the high-dose group but caused no effects on litter size, weaning index, and sex ratio. Similarly, the continued exposure of F₁ parental rats to ZnCl₂ also reduced fertility, liter size, viability (day 0), and the body weight of F₂ pups within the high-dose group but caused no effects on weaning index and sex ratio. Exposure of ZnCl₂ to F₀ and F₁ parental males resulted in a significant reduction in their body weights, and the F₀ and F₁ parental females did not show any significant difference in their body weights compared to their control groups. However, the postpartum dam weights of both F₀ and F₁ female rats were significantly reduced compared to their controls. Exposure of ZnCl₂ to F_o and F₁ generation parental rats did not produce any significant change of their clinical signs as well as their clinical pathology parameters, except the alkaline phosphotase (ALK) level, which showed an upward trend in both sexes of both generations. Exposure of ZnCl₂ to F₀ rats resulted in a reduction of brain, liver, kidney, spleen and seminal vesicles weights of males and in the spleen and uterus of females. Similarly, exposure of F₁ rats to ZnCl₂ also resulted in reduction of brain, liver, kidney, adrenal, spleen, prostate and seminal vesicles weights of males and in spleen and uterus of females. ZnCl₂ exposure resulted in grossly observed gastro-intestianla (GI) tract, lymphoreticular/hematopoietic, and reproductive tract lesions in parental rats in both generations. Reduced body fat was also recorded in F₁ parental rats.     

Chlortetracycline and tylosin runoff from soils treated with antimicrobial containing manure

This study assessed the runoff potential of tylosin and chlortetracycline (CTC) from soils treated with manure from swine fed rations containing the highest labeled rate of each chemical. Slurry manures from the swine contained either CTC at 108 μ g/g or tylosin at 0.3 μ g/g. These manures were surface applied to clay loam, silty clay loam, and silt loam soils at a rate of 0.22 Mg/ha. In one trial, tylosin was applied directly to the soil surface to examine runoff potential of water and chemical when manure was not present. Water was applied using a sprinkler infiltrometer 24-hr after manure application with runoff collected incrementally every 5 min for about 45 min. A biofilm crust formed on all manure-treated surfaces and infiltration was impeded with > 70% of the applied water collected as runoff. The total amount of CTC collected ranged from 0.9 to 3.5% of the amount applied whereas tylosin ranged from 8.4 to 12%. These data indicate that if surface-applied manure contains antimicrobials, runoff could lead to offsite contamination.     

Assessment of imidacloprid toxicity on reproductive organ system of adult male rats

In the current study it was aimed to investigate the toxicity of low doses of imidacloprid (IMI) on the reproductive organ systems of adult male rats. The treatment groups received 0.5 (IMI-0.5), 2 (IMI-2) or 8 mg IMI/kg body weight by oral gavage (IMI-8) for three months. The deterioration in sperm motility in IMI-8 group and epidydimal sperm concentration in IMI-2 and IMI-8 groups and abnormality in sperm morphology in IMI-8 were significant. The levels of testosterone (T) and GSH decreased significantly in group IMI-8 compared to the control group. Upon treatment with IMI, apoptotic index increased significantly only in germ cells of the seminiferous tubules of IMI-8 group when compared to control. Fragmentation was striking in the seminal DNA from the IMI-8 group, but it was much less obvious in the IMI-2 one. IMI exposure resulted in elevation of all fatty acids analyzed, but the increases were significant only in stearic, oleic, linoleic and arachidonic acids. The ratios of 20:4/20:3 and 20:4/18:2 were decreased and 16:1n-9/16:0 ratio was increased. In conclusion, the present animal experiments revealed that the treatment with IMI at NOAEL dose-levels caused deterioration in sperm parameters, decreased T level, increased apoptosis of germ cells, seminal DNA fragmentation, the depletion of antioxidants and change in disturbance of fatty acid composition. All these changes indicate the suppression of testicular function.     

The characteristics of nitrate removal by the psychrotolerant denitrifying bacterium Acinetobacter johnonii DBP-3, isolated from a low-temperature eutrophic body of water

A psychrotolerant denitrifying bacterial strain, DBP-3, was isolated from a eutrophic body of water by low-temperature-oriented acclimation culture. Based on its morphologicalandbiochemicalcharacteristics and 16S rDNA gene sequence, the bacterium was identified as belonging to the genus Acinetobacter and closely related to A. johnonii. The satisfactory growth of DBP-3 was observed at 10–30°C and pH 7–9. Strain DBP-3 was able to utilize three types of carbon sources (sodium acetate > sodium citrate > glucose) to support growth and denitrification. DBP-3 grew faster, but with lower nitrate removal efficiency and higher nitrite accumulation, under aerobic conditions than under anoxic conditions. DBP-3 was extremely susceptible to tetracycline and rifampicine and less sensitive to ampicillin and penicillin. The growth of DBP-3 was significantly affected by Hg (II), Cr (VI), Pb (II), Cd (II), and As (III) at 0.32, 0.63, 1.25, 2.5, and 25.0 mg L^?1, respectively. Interestingly, chromium (VI) significantly promoted DBP-3 growth at concentrations lower than 0.32 mg L^?1. These data may be helpful to support the use of strain DBP-3 in the purification of eutrophic water bodies at low temperatures.     

Comparative effect of thymol or its glucose conjugate,thymol-β-d-glucopyranoside,on Campylobacter in avian gut contents

Campylobacter jejuni is an important human food-borne pathogen that can contaminate meat and poultry during processing. Consequently, strategies are sought to reduce the carriage of C. jejuni in food animals before they arrive at the abattoir. Thymol is a natural product that reduces survivability of Campylobacter in vitro, but its rapid absorption from the proximal alimentary tract limits its bactericidal efficacy in vivo. Thymol-β-d-glucopyranoside is more resistant to absorption than free thymol, but its administration to chickens has not been reported. In the present studies, 1 mM thymol-β-d-glucopyranoside was shown to exhibit near equal anti-Campylobacter activity as 1 mM thymol when incubated anaerobically in avian crop or cecal contents in vitro, resulting in reductions of 1.10–2.32 log₁₀ colony forming units mL^?1 in C. jejuni concentrations after 24 h incubation. In a follow-up live animal study, oral administration of thymol-β-d-glucopyranoside, but not free thymol, significantly lowered (>10-fold) recovery of Campylobacter from the crop of market-aged broilers when compared to placebo-treated controls (n = 6 broilers/treatment). Neither thymol-β-d-glucopyranoside nor thymol affected recovery of Campylobacter from cecal contents of the treated broilers. These results indicate that rapid absorption or passage of free thymol from the crop precluded its anti-Campylobacter activity at this site and throughout the entire gastrointestinal tract. Conversely, lower recovery of Campylobacter from the crop of birds treated with thymol-β-d-glucopyranoside indicates this conjugate was retained and able to be hydrolyzed to biologically active free thymol at this site as intended, yet was not sufficiently protected to allow passage of efficacious amounts of the intact glycoside to the lower gut. Nevertheless, these results warrant further research to see if higher doses or encapsulation of thymol-β-d-glucopyranoside or similar glycosides may yield an efficacious additive to reduce carriage of Campylobacter as well as other pathogens throughout the avian gut.     

Speciation of Arsenic in Ambient Aerosols Collected in Los Angeles

First-time measurements of the potentially toxic inorganic species of arsenic (arsenite arid arsenate) have been obtained in fine (<2.5 µm AD) and coarse (>2.5 µm AD) atmospheric particles in the Los Angeles area. A recently developed method that includes procedures for sample collection, preparation, and analysis was used in this study. Size-fractlonated aerosol samples were collected with a high-volume dichotomous virtual impactor that employed polytetrafluoroethylene filters. Results were obtained for the recovery of arsenic standards added to unexposed and collected filters. Data from this study, indicated that the recently developed speciation method can be used to determine concentrations of As(lll) and As(V) In atmospheric particulate matter samples.

Size-fractionated aerosol samples were collected in the city of Industry during January and February 1987. In most samples, As(lll) and As( V) were above the detection limit (approximately 1 ng m^-3 of either species) in both aerosol size fractions. A greater portion (about 75 percent) of the two species were observed in the fine particles. The As(lll)/As(V) ratio for both particle sizes was close to 1 (I.e., an equal mixture of both species). Comparison of total suspended particulate arsenic measured by the speciation method to that measured by a routine California Air Resources Board-approved procedure showed good agreement (r = 0.94), indicating both methods were approximately equivalent for the collection and analysis of aerosol arsenic.