Evaluation of the toxicity of tetrabromobisphenol A and some of its oxidation products using a micro-scale algal growth inhibition test

A micro-scale algal growth inhibition (μ-AGI) test using a common micro-plate based fluorometric detection was used to demonstrate the effects of humic substances (HSs) on the toxicity of tetrabromobisphenol A (TBBPA) and its oxidative decomposition products 2,5-dibromo-1,4-benzoquinone (2,5-DBBQ), 2,5-dibromohydroquinone (2,5-DBHQ), 2,6-dibromobenzoquinone (2,6-DBBQ), and 2,6-dibromophenol (2,6-DBP) to Pseudokirchneriella subcapitata. The EC₅₀ values were: EC_50(TBBPA) = 7 mg L^?1, EC_50(2,5-DBHQ) = 7 mg L^?1, EC_50(2,5-DBBQ) = 19 mg L^?1, EC_50(2,6-DBP) = 49 mg L^?1, and EC_50(2,6-DBBQ) = 13 mg L^?1. The toxicity of the chemicals was slightly lower in the presence of HA. The toxicity of TBBPA decomposed by a biomimetic catalytic system consisting of iron (III) 5,10,15,20-tetrakis (p-sulfonatophenyl) porphyrin (Fe(III)-TPPS) and KHSO₅ was also evaluated using P. subcapitata and Chlamydomonas reinhardtii.     

Degradation of bisphenol A by photo-fenton processes

The photo-Fenton reactions, which could yield hydroxyl radicals via the catalytic degradation of H₂O₂ by Fe(II), were focused as one of the abiotic degradation processes of bisphenol A (BPA) in surface waters. At pH 6, in the presence of H₂O₂ only, 32% of BPA was degraded after 120?min of irradiation. However, 97% of BPA was degraded in the presence of both H₂O₂ and Fe(II). Without light irradiation, no BPA degradation was observed even in the presence of Fe(II) and H₂O₂. These results show that photo-Fenton processes are effective in the natural attenuation of BPA in surface water. In addition, the presence of humic acids (HAs), which were of more aliphatic nature, resulted in enhancing BPA degradation via the photo-Fenton processes. Therefore, HAs can be one of the important factors in enhancing the degradation of BPA in surface water via the photo-Fenton processes.     

Coagulation characteristics of humic acid modified with glucosamine or taurine

To suppress the coagulation of humic acid (HA) in aqueous solutions, HA was modified with hydrophilic amines, such as glucosamine or taurine. These amines were attached to carboxyl groups in HA via amide bond formation. The degree of modification (R(m)) was estimated to be 21-38%. Infrared spectra of the modified HAs were also consistent with the presence of amide bonds. Acid-base titration showed that the average acid-dissociation constant (pK(app)) of the HA samples was increased by the modification. The Ca(2+) binding capacity of HA decreased with an increase in R(m) value. Critical pH or Ca(2+) concentration, at which HA coagulation occurs, was increased as the result of the modification. These critical points for taurine-HA were higher than those for glucosamine-HA. This is mainly due to electrostatic repulsion by sulfonate groups in taurine. These results indicate that the coagulation of HA is suppressed by modifying the molecules with glucosamine or taurine.     

Study on 14C-BHA absorption and distribution in rat

BHA was administered to rats at doses of 5 or 500 mg/kg for seven days. ¹⁴C-BHA absorption was investigated on the eighth day and compared with animals receiving a single dose of 5 or 500 mg/kg BHA. Absorption of ¹⁴C-BHA was proportionately greater at the high dose rats. ¹⁴C distribution was 3–6 times higher in the forestomach than in the pyloric region of the stomach. The urinary excretion of BHA conjugates was not dependent on pretreatment with BHA or on the dose.     

A practical and simple method in fractional determination of ambient forms of mercury in air

A collecting method to prepare a fractional determination of ambient forms of mercury in air is proposed. Particulate mercury is collected by a glass fiber filter. Sequential trap tubes consist of four long and slender quartz tubes, in which the Chromosorb W treated with HC$\text{l}$ gas for Hg(II), the Chromosorb W treated with 0.1 M NaOH for methylmercury, the silver-wire tip for metallic mercury and the gold plate tip for dimethylmercury are packed. The collection efficiency for these trap tubes was in the range of about 85 ～ 100% at the μg or ng concentration level. With this method, the air was collected by suction at the rate of 1.5 $\text{l}$/min. for about five hours, the detection limit being 0.2 ng Hg/m³. The results indicate that the regional distribution of total mercury in air was considerably greater in the volcanic and hot spring regions. Mercury species was found to be mostly Hg(II), followed by metallic mercury, methylmercury, dimethylmercury and particulate mercury in this order.     

Effect of humic acids on the toxicity of pollutants to Chlamydomonas reinhardtii: Investigation by a microscale algal growth inhibition test

Dissolved humic substances (DHSs) are the major components of organic matter in the aquatic environment. DHSs are well known to considerably affect the speciation, solubility, and toxicity of a wide variety of pollutants in the aquatic environment. In this study, the effects of the toxicity of heavy metals and hydrophobic organic pollutants (HOPs) on Chlamydomonas reinhardtii in the presence of humic acid (HA) were examined by a microscale algal growth inhibition (μ-AGI) test based on spectrophotometric detection. To clarify the relationship between the chemical properties of HAs and the toxicity change of pollutants, eight HAs from different sources were prepared and used. HAs were responsible for mitigating the toxicity of Hg, Cu, pesticides (γ-HCH, 2,4-D, and DDT), and polycyclic aromatic hydrocarbons (PAHs) such as naphthalene (Nap), anthracene (Ant), and benzo[a]pyrene (BaP). In particular, an approximately 100-fold decrease in the toxicity of BaP was observed in the presence of 10 ppm HAs extracted from tropical peat. The results indicated that the carboxylic group content and the HA molecular weight are correlated to the changes in the heavy metal toxicity. For HOPs, the aromaticity and polarity of HAs are crucial for mitigating their toxicity. Furthermore, it was clearly shown that the lake water including a high concentration of DHSs collected from Central Kalimantan, Indonesia, reduced the toxicity of Hg and γ-HCH on Chlamydomonas reinhardtii.

Graphical abstract

     

Analysis of the migration of instantaneously injected cesium in artificial fractures of Lac du Bonnet granite, Manitoba, Canada

Breakthrough curves of ¹³⁷Cs and tritiated water injected instantaneously into artificial fractures in Lac du Bonnet granite were analyzed using the analytical solution for a single rock-fracture system and assuming the linear sorption isotherm of the solute. Parameters of nuclide diffusion and sorption in rock matrices, obtained by fitting, varied depending on the flow velocity in the fractures. According to theoretical calculations, different fracture flow velocities lead to different diffusion distances of nuclides in matrices at the same injection volume. As microscopic inhomogeneity is considered to exist in the rock matrix, the average diffusion-sorption characteristics of the matrix within the diffusion distance may have varied with the fracture flow velocity. Surface sorption was marked in fractures that had relatively high matrix sorption-diffusion capacities. The phenomenon was interpreted using the theoretical relationships developed between the surface sorption, matrix sorption and pore diffusion coefficient, and the porosity of matrices.The effect of the nonlinear sorption of solute was examined by numerically solving model equations that incorporate the nonlinear isotherm. This incorporation may contribute to the reduction of deviations between theoretical and experimental BTC's.     

Studies on the coupling product between oxidation products derived from pentachlorophenol and cyclodextrins

The coupling products (CPs), which were formed via the peroxosulfate catalyzed oxidation of pentachlorophenol (PCP) with iron(III)-tetrakis(sulfonatophenyl)porphyrin (Fe(III)-TPPS) in the presence of hydroxypropyl-beta -cyclodextrin (HP-beta -CD) or HP-gamma -CD, were separated by ultrafiltration from the reaction mixture. When the percentages of chlorine species in the reaction mixture were calculated from the concentrations of organic chlorine in the reaction mixture and CPs, 10-25% of chlorine species in the reaction mixture was organic chlorine that was incorporated into CDs. Analyses of the CPs by pyrolysis-GC/MS (Py-GC/MS) and 13C NMR showed that the PCP-derived products were covalently incorporated into the CDs. To evaluate the acute toxicity of the CPs, a Microtox test was examined. Toxicities of the CPs were reduced slightly, compared to the controls (PCP alone and PCP + reaction blanks). In the reaction blanks, mesaconic acid (MA) moieties were detected as a result of the oxidation of CDs in the absence of PCP. Thus, factors in the toxicities, detected in the CPs, can be attributed to the oxidation products derived from CDs, such as MA, as well as the PCP-derived products incorporated into the CDs.     

Effect of ZnCl<Subscript>2</Subscript> impregnation ratio on pore structure of activated carbons prepared from cattle manure compost: application of N<Subscript>2</Subscript> adsorption-desorption isotherms

Activated carbons were prepared from cattle manure compost (CMC) by ZnCl₂ activation with various ZnCl₂/CMC mass ratios. Based on the N₂ adsorption-desorption isotherms, mathematical models including the Dubinin-Radushkevich (DR) equation, the α_s plot, and the Horvath-Kawazoe method were used to analyze the pore structural characteristics of the prepared activated carbons. It was found that for carbons possessing both micro-and mesopores, the DR method provided a more accurate estimation than the α_s method for the extent of microporosity. The effect of the ZnCl₂ impregnation ratio on the pore structure was discussed using the DR method. The results revealed that pore evolution involved three distinct regions with increases in the amount of impregnated ZnCl₂: raising the ZnCl₂/CMC mass ratio from 0.00 to 0.50 resulted in a 19-fold increase in micropore volume (V_me ^D) but caused no change in the mesopore volume (V_me ^D); increasing the ZnCl₂/CMC mass ratio from 0.50 to 1.00 led to an increment in V_mi ^D of about 50% and in V_me ^D of 170%; while raising the ratio from 1.50 to 2.50 caused a slight decrease in V_mi ^D but a 200% increment in the value of V_me ^D.