The occurrence, distribution and removal of adsorbable organic halogens (AOX) in a typical fine chemical industrial park.

Coastal water quality in China has been impacted by direct discharge of industrial wastewater, and various kinds of AOX pollutants have been detected in the seawater and sediment. As the dominant pollution source of Hangzhou Bay, a typical fine chemical industry park "HSEDA" was selected as the study area in this research. The AOX in both wastewater and sludge phases from 22 large-scaled enterprises were simultaneously investigated. The results quantitatively illustrated the AOX flows from engineered wastewater and sludge treatment systems to natural environment. It can be seen that industrial enterprises discharged at least 160 t AOX every year, and about 105.4 t/a AOX eventually entered the natural environment. The dye manufacturing industry, which accounted for more than 60% of the total AOX emission load in HSEDA, was identified as the AOX pollution-intensive sector. The occurrence, characteristic pollutants and fate of AOX in dye wastewater were discussed, on the basis of which the improvements of cleaner production and wastewater treatment technologies have been put forward.

Ozone oxidation of 2,4,6-TCP in the presence of halide ions: Kinetics, degradation pathways and toxicity evaluation.

2,4,6-Trichlorophenol (2,4,6-TCP) is extensively consumed in industrial production and may cause environmental damages. The effect of halide ions on the decomposition of 2,4,6-TCP has often been overlooked. In this study, the bromide ion was found to have a stronger negative impact on 2,4,6-TCP degradation than chloride ion in the O3 system, and led to the formation of adsorbable organic halogens (AOX). Kinetic modeling demonstrated that the concentration of various radicals was largely depended on the solution pH, and stronger basicity not only contributed to the mineralization of 2,4,6-TCP, but also inhibited the formation of halogenated by-products. Combining the intermediate identification and quantum chemical calculation, the degradation pathways of 2,4,6-TCP during ozone oxidation process were proposed. The toxicity test and ECOSAR simulation demonstrated that the acute toxicity of some 2,4,6-TCP degradation intermediates was relatively higher than their parent compound. With high concentrations of halide ions, the ozone-treated solution showed greater toxicity than the originator 2,4,6-TCP solution. These results illustrate that the ozone treatment of the halide-containing wastewater may cause potential ecological hazards and its application needs to be more cautious.

Combined effect of polystyrene microplastics and dibutyl phthalate on the microalgae Chlorella pyrenoidosa.

The combined effect of polystyrene microplastics (mPS) and dibutyl phthalate (DBP), a common plastic additive, on the microalgae Chlorella pyrenoidosa was investigated in the present study. The 96 h-IC50 value of DBP was 2.41 mg L-1. Polystyrene microplastics exhibited size-dependent inhibitory effect to C. pyrenoidosa, with the 96 h-IC50 at 6.90 and 7.19 mg L-1 for 0.1 and 0.55 µm mPS respectively, but little toxicity was observed for 5 µm mPS. The interaction parameter ρ based on the response additive response surface (RARS) model varied from -0.309 to 5.845, indicating the interaction pattern varying with exposure concentrations of chemical mixtures. A modified RARS model (taking ρ as a function of exposure concentration) was constructed and could well predict the combined toxicity of mPS and DBP. More than 20% reduction of DBP was observed at 20 mg L-1 mPS, while 1 mg L-1 mPS had no significant effect on the bioavailability of DBP at different sampling time points. Volume, morphological complexity and chlorophyll fluorescence intensity of microalgal cells were disturbed by both DBP and mPS. The antagonistic effect of high concentrations of mPS might be partially attributed to the combination of hetero- and homo-aggregation and the reduced bioavailability of DBP. The overall findings of the present study profiled the combined toxic effects of mPS and DBP on marine phytoplankton species which will be helpful for further evaluation of ecological risks of mPS and DBP in marine environment.

The effect of polystyrene plastics on the toxicity of triphenyltin to the marine diatom Skeletonema costatum-influence of plastic particle size.

The effect of polystyrene (PS) particles on the toxicity of triphenyltin (TPT) to the marine diatom Skeletonema costatum was investigated. The 0.1-µm PS particles attached to the cell walls of S. costatum but did not cause adverse effects on the growth of the diatom. The adsorption of TPT to PS particles was negligible in seawater systems, but the presence of 0.1-µm PS significantly reduced the bioavailable concentrations of TPT in f/2-Si medium, indicating a potential three-way interaction between TPT, PS particles, and components of f/2-Si medium. The adsorption of TPT to PS of smaller size (i.e., 0.1 µm) was stronger than that of PS of larger size (i.e., 5 µm), which was probably attributed to larger surface areas of smaller PS particles. The presence of PS could reduce the toxicity of TPT. IC50 values of TPT increased from 0.56 to 0.85 and 0.71 µg/L at the presence of 20 mg/L 0.1-µm PS and 5-µm PS, respectively. The overall results of this study profiled the combined toxic effects of PS and TPT on marine phytoplankton species and highlighted the difference in adsorption of organic pollutants by microplastics in different ambient mediums.

Effect of Multi-walled Carbon Nanotubes on the Toxicity of Triphenyltin to the Marine Copepod Tigriopus japonicus.

Marine organisms are often exposed to a mixture of various pollutants in marine environment (i.e., nanoparticles, organic pollutants). The present study investigated the potential effects of multi-walled carbon nanotubes (MWCNTs) on the toxicity of triphenyltin chloride (TPTCl). The results revealed an antagonistic interaction between MWCNTs and TPTCl on the copepod through 96 h acute exposure, which was attributed to the adsorption of TPTCl to MWCNTs and aggregation of MWCNTs in the test solutions. Results of 21 days' chronic exposure showed that the effect concentration of MWCNTs could be 100 times lower than that of acute exposure. The exposure to binary mixture of MWCNT (1.0 mg/L) and TPTCl (0.3 µg/L) caused a reduction by 94% for the 3rd time spawning and 83% for the total number of hatched nauplii. The ingestion and exterior attachment of MWCNTs to the copepod might be the main reasons causing the adverse effect in reproduction.

Effect of nano zinc oxide on the acute and reproductive toxicity of cadmium and lead to the marine copepod Tigriopus japonicus.

Given the absorbability of nZnO and its inevitable coexistence with trace metals such as Cd and Pb in coastal environment, nZnO can adsorb these pollutants thereby affecting their distribution in different media of marine ecosystem. The marine copepod Tigriopus japonicus was applied in the present study to investigate the combined effect of nZnO and Cd or Pb on mortality and reproduction in marine organisms. For acute exposure, presence of 1.0 mg/L nZnO increased the toxicity of both Cd and Pb, as their LC50 decreased from 5.9 and 75.4 mg/L to 3.95 and 48.0 mg/L, respectively. For 21 d chronic exposure, the reproduction of the copepod was influenced by Cd and Pb at environmental relevant concentrations, and the interaction between nZnO and Cd or Pb appeared to be antagonistic. The waterborne Cd and Pb concentration was affected by nZnO for neither acute nor chronic exposure, indicating no adsorption of these two metals to nZnO at relative low concentration. The overall findings of this study suggested the binary exposure to nZnO/Cd or nZnO/Pb might have potential different toxic mechanisms between acute and chronic exposure.

Combined effect of polystyrene plastics and triphenyltin chloride on the green algae Chlorella pyrenoidosa.

The combined effect of polystyrene (PS) particles and triphenyltin chloride (TPTCl) to the green algae Chlorella pyrenoidosa was studied. The 96 h IC50 of TPTCl to the green algae C. pyrenoidosa was 30.64 µg/L. The toxicity of PS particles to C. pyrenoidosa was size-dependent, with the 96 h IC50 at 9.10 mg/L for 0.55 µm PS but no toxicity observed for 5.0 µm PS. The exposure to 0.55 µm PS led to damage on structure of algal cells, which could in turn cause inhibition on photosynthesis and population growth of the green algae. TPTCl concentrations in test medium were lowered by 15-19% at presence of 0.55 µm PS particles, indicating a reduced bioavailability of TPTCl. In spite of this reduced bioavailability, the presence of PS increased the toxicity of TPTCl, which might be attributed to facilitated uptake of TPTCl by the green algae after the damage of cell structure. The overall results of the present study provided important information on the effect of PS on the bioavailability and toxicity of TPTCl to phytoplankton species.

Toxic effect of triphenyltin in the presence of nano zinc oxide to marine copepod Tigriopus japonicus.

Marine organisms are naturally exposed to different environmental pollutants including organic pollutants and nanoparticles. The interactive effects between nanoparticles and other chemicals on aquatic organisms have raised concerns regarding the potential of nanomaterials as the vector for other chemicals. In the present study, the effect of nano zinc oxide (nZnO) on the bioavailability of triphenyltin chloride (TPTCl) was studied, and their combined acute and reproductive toxicity to the marine copepod Tigriopus japonicus were evaluated. At experimental concentration ranges of nZnO in this study, the percentage of dissolution of Zn2+ was relative stable (from 62% to 66%), and nZnO did not affect the bioavailability of TPTCl to the copepods. The acute toxicity of binary mixtures of nZnO/TPT was equivalent to that of the mixture of Zn2+/TPT. In agreement with the decrease in TPTCl's LC50 values at the presence of nZnO, their interacting effect was synergistic based on response addition response surface model, and the interacting parameter was modelled to be -1.43. In addition to acute toxicity test, reproductive toxicity tests revealed that exposure to nZnO and TPTCl didn't affect the successful mating rate and the number of nauplii in the 1st brood, but they extended the time for the eggs to hatch from 2.53 days to 3.94 and 3.64 days, respectively. The exposure to nZnO/TPTCl mixture delayed the time to hatch to 5.78 days.