Degradation of octylphenol and nonylphenol by ozone - part I: direct reaction

This aqueous reaction between ozone and two alkylphenols (APs), namely octylphenol (OP) and nonylphenol (NP), has been investigated. Both compounds are important endocrine disrupting chemicals, which arise from the biodegradation of alkylphenol ethoxylates and are often found at relatively high concentrations in wastewater effluents. In this paper the results of an experimental study are presented which provide values for the reaction rate constants between molecular ozone and undissociated OP and NP, and overall reaction rate constants for the degradation of the two APs at pH values in the range of 7-9. The kinetic rate constants for OP and NP degradation by molecular ozone were 4.33(+/-0.18) x 10(4) and 3.90(+/-0.10) x 10(4) M(-1) s(-1), and the reaction stoichiometry was similar in both cases and equal to approximately 1.3:1 ([O3]:[AP]). The overall second order reaction rate constants for the two APs increased significantly with increasing pH, which is believed to be mainly due to the increasing influence of indirect radical reaction with increasing pH; this aspect is considered in more detail in a companion paper. A preliminary investigation of the reaction mechanism suggests that an initial product of ozonation is hydroxyl-alkyl phenol.     

Decolorization of cationic red X-GRL by wet air oxidation: performance optimization and degradation mechanism

The decolorization of a strong colored azo dye solution of cationic red X-GRL was investigated by wet air oxidation under relatively mild conditions (60-180 degrees C, PO2 = 0-1.2 MPa). Mono-factor experiments were carried out to investigate the effect of the operation factors and the relatively important parameters were selected for optimization using response surface methodology to explore the interactions of these relatively important parameters. Model regeneration analysis and the check experiments showed that the data of the general linear model agreed with the experiment results well. With multistage Monte-Carlo optimization, the best region of these variables could be predicted to dye color removal. At typical operational conditions, the intermediates of dye degradation were detected and confirmed by GC/MS system. Considering the intermediates and the structure analysis with the help of Gaussian 03W (version 6.0) and the theory of dye color, a possible degradation mechanism for the wet air oxidation of cationic red X-GRL was discussed and the probable degradation pathway was deduced.     

Influence of the DMPP (3,4-dimethyl pyrazole phosphate) on nitrogen transformation and leaching in multi-layer soil columns

The application of nitrogen fertilizers leads to various ecological problems such as nitrate leaching. The use of nitrification inhibitors as nitrate leaching retardants is a proposal that has been suggested for inclusion in regulations in many countries. In this study, using a multi-layer soil column device, the influence of new nitrification inhibitor DMPP (3,4-dimethyl pyrazole phosphate) was studied for understanding the nitrogen vertical transformation and lowering the nitrate leaching at different soil profile depths. The results indicated that, within 60 d of experiment, the regular urea added 1.0% DMPP can effectively inhibit the ammonium oxidation in the soil, and improve the ammonium concentration in soil solution over the 20cm depths of soil profile, while decline the concentrations of nitrate and nitrite. No obvious difference was found on ammonium concentrations in soil solution collected from deep profile under 20cm depths between regular urea and the urea added 1.0% DMPP. There was also no significant difference for the nitrate, ammonium and nitrite concentrations in the soil solution under 40cm depths of soil profile with the increasing nitrogen application level, among the treatments of urea added 1.0% DMPP within 60 d. It is proposed that DMPP could be used as an effective nitrification inhibitor in some region to control ammonium oxidation and decline the ion-nitrogen leaching, minimizing the shallow groundwater pollution risk and being beneficial for the ecological environment.     

The study of distribution and fate of nitrobenzene in a water/sediment microcosm

In November 2005, an explosion occurred at a petrochemical plant of the Jilin Petrochemical Corporation in Jilin Province, China. A nearby water body was seriously polluted with a large spill of toxic substances made up of a mixture of benzene, aniline, and nitrobenzene (NB). To understand the long term impact of NB on public health and ecosystem around the Songhua River, it was necessary to investigate its fate in the environment. In this study, a microcosm was used to mimic the polluted water system and to study the transport and fate of NB in the river water body. The volatility and biodegradation of NB was investigated and a Markov model was applied to predict the fate of NB in the environment. The simulated results matched very well with the results obtained from the microcosm experiment. The model indicated that at room temperature and after around 500 h, there was only residual NB in the water and sediment. Most of the NB (around 82%) evaporated into the air and 18% was degraded by microorganisms.     

Zinc and cadmium accumulation and tolerance in populations of Sedum alfredii

To investigate the variation of Zn and Cd accumulation and tolerance of Sedum alfredii (a newly reported Zn/Cd hyperaccumulator), field surveys and hydroponic experiments were conducted among three populations of this species: two originating from old Pb/Zn mines in Zhejiang (ZJ) and Hunan (HN) Provinces and one from a "clean" site in Guangdong (GD) Province, China. Under field conditions, up to 12,524 and 12,253 mg kg(-1) Zn, and 1400 and 97 mg kg(-1) Cd in shoots of ZJ and HN plants were recorded respectively. Under hydroponic conditions, ZJ and HN plants accumulated significantly higher Zn and Cd in their leaves and stems, and possessed significantly higher Zn and Cd tolerance than GD plants. Among the two contaminated populations, ZJ plants showed higher Cd tolerance and accumulation (in leaves) than HN plants. The present results indicate that significant differences in Zn and Cd accumulation and tolerance exist in populations of S. alfredii.     

In situ studies on the distribution patterns and dynamics of microcystins in a biomanipulation fish--bighead carp (Aristichthys nobilis)

The distribution and dynamics of microcystins in various organs of the phytoplanktivorous bighead carp were studied monthly in Lake Taihu, which is dominated by toxic cyanobacteria. There was a good agreement between LC-MS and HPLC-UV determinations. Average recoveries of spiked fish samples were 63% for MC-RR and 71% for MC-LR. The highest MC contents in intestine, liver, kidney and spleen were 85.67, 2.83, 1.70 and 1.57 microg g-1 DW, respectively. MCs were much higher in mid-gut walls (1.22 microg g-1 DW) than in hind- and fore-gut walls (0.31 and 0.18 microg g-1 DW, respectively), suggesting the importance of mid-gut wall as major site for MC absorption. A cysteine conjugate of MC-LR was detected frequently in kidney. Among the muscle samples analyzed, 25% were above the provisional tolerable daily intake level by WHO. Bighead is strongly resistant to microcystins and can be used as biomanipulation fish to counteract cyanotoxin contamination in eutrophic waters.     

On the presence of enriched amounts of 235U in hot particles from the terrestrial area affected by the Palomares accident (Spain)

The characterisation by ICP-MS of an isolated Pu-U hot particle originating from the nuclear weapons accident in Palomares (Spain) shows, for the first time, that its uranium content is highly enriched in (235)U. The enrichment has been confirmed by independent analyses of two surface soil samples collected in a heavily contaminated area close to the impact point of one of the bombs. This finding clarifies better the composition of the weapons involved in the accident and is of importance when the inventory of U and Pu in the contaminated area are to be calculated.     

Temporal change in the distribution patterns of hexachlorobenzene and dichlorodiphenyltrichloroethane among various soil organic matter fractions

Residence time-dependent distribution patterns of hexachlorobenzene (HCB) and dichlorodiphenyltrichloroethane (DDT) among different soil organic matter fractions of three Chinese soils were investigated. Soil organic matter (SOM) was fractionated into fulvic acid (FA), humic acid (HA), bound-humic acid (BHA), lipid, and insoluble residue (IR) fractions using methyl isobutyl ketone (MIBK) method. Results revealed that as the residence time prolonged, the amounts of HCB and DDT in the FA, HA and BHA fractions decreased, while those in the lipid and IR fractions increased. One- and two-compartment first order, and one- and two-parameter pore-diffusion kinetic models were used to describe the mobility of HCB and DDT from the FA, HA and BHA fractions. The results suggest that excellent agreements were achieved between the experimental data and fits to the two-compartment first order kinetic model (R2>0.97). The transfer rates of HCB and DDT followed the order FA>HA>BHA.     

Modification of ferrite–manganese oxide sorbent by doping with cerium oxide

Fe–Mn oxide and Ce-doped Fe–Mn oxide sorbents were studied on the structural and desulfurization behavior in COS removal from syngas. The effects of cerium oxide on the Fe–Mn oxides have been investigated by XRD, BET, TPR, XPS and TEM methods. Analysis data show that the Ce-doped sorbent has larger specific surface area and better particles’ dispersion compared with non-modified Fe–Mn sorbent. The addition of Ce improves the reduction performance of Fe–Mn species. The desulfurization experiments show that the desulfurization activity of sorbent can be increased because of the promotion of the structural and redox properties by ceria doped. The Ce-doped sorbent can reduce COS from 15,000 ppmv to less than 0.1 ppmv at 325 °C and a space velocity of 1000 h⁻¹.