PURPOSE: In this study, we determined normal serum butyrylcholinesterase (BChE) and carboxylesterase (CbE) activities in Tupinambis merianae in order to obtain reference values for organophosphorus pesticide monitoring. METHODS: Forty-two T. merianae individuals were grouped by sex and size to identify potential differences in their enzyme levels to allow for proper representation of normal values for females, males, juveniles, and hatchlings. Mean CbE was determined using two model substrates: alpha-naphtylacetate (α-NA) and p-nitrophenyl valerate (4-NPV). BChE and CbE sensitivity to malaoxon (Mx) was also evaluated as well as the possibility of BChE reactivation with pyridine-2-aldoxime methochloride (2-PAM). RESULTS: Mean adult females’ BChE was significantly higher than adult males, juveniles, and hatchlings. No significant differences were found between groups regarding CbE. CbE (4-NPV) activity showed slightly negative correlation with lizard snout–vent length, while BChE and CbE (α-NA) showed no correlation with body size. Apparent IC50 values for BChE and CbE (α-NA) suggested different sensitivities among groups. CbE (4-NPV) could not be inhibited. All Mx-inhibited groups treated with 2-PAM in a final concentration of 2.8 mM showed clear signs of reactivation. CONCLUSIONS: In conclusion, the results demonstrate that (1) plasma esterase activity did not vary with age and sex, except for BChE activity, and (2) because biological and environmental variables could be confounding factors in the response of plasma cholinesterases, complementary biomarkers like CbE inhibition and oxime-induced reactivation of esterases are strongly recommended.

The aim of the present study was to show a relationship between toxicity of 100-fold concentrated water and aquatic habitat conditions. Environmental waters are 100-fold concentrated with solid-phase extraction. Medaka early fry was exposed in these waters for 48 h. The number of death and disorder was counted at 1, 2, 3, 6, 12, 24, and 48 h; toxicity was expressed using inverse median effect time and median lethal time (ET ₅₀ ⁻¹ , LT ₅₀ ⁻¹ ). Average score per taxon (ASPT) for benthic animals and Index of Biotic Integrity (IBI) for fish were applied as indices of aquatic habitat conditions. The results of toxicity test were compared using ASPT and IBI. The different levels of toxicity were detected in the seawater of Japan. At the Husino River area, toxicity cannot be detected. In rivers, high toxicity appeared at urban districts without sewerage. By Spearman coefficient, the relationship between toxicity and high biochemical oxygen demand (BOD) were obtained. BOD household wastewater contains hydrophobic toxic matters; otherwise, seawater in industrial area does not show clear relationship between toxicity and chemical oxygen demand. Gas chromatography to mass spectrometry simultaneous analysis database may give an answer for the source of toxicity, but further test is required. Ratio of clear stream benthic animal sharply decreased over 0.25 of LT ₅₀ ⁻¹ or 0.5 of ET ₅₀ ⁻¹ . Tolerant fish becomes dominant over 0.3 of LT ₅₀ ⁻¹ or 0.5–1.0 of ET ₅₀ ⁻¹ . By Pearson product–moment correlation coefficient, correlation coefficient between toxicity and ASPT was obtained at −0.773 (ET ₅₀ ⁻¹ ) and −0.742 (LT ₅₀ ⁻¹ ) at 1 % level of significance with a high negative correlation. Toxicity (LT ₅₀ ⁻¹ ) has strong correlation with the ratio of tolerant species. By Pearson product–moment correlation coefficient, correlation coefficient between toxicity and IBI obtained were −0.155 (ET ₅₀ ⁻¹ ) and −0.190 (LT ₅₀ ⁻¹ ) at 1 % level of significance and has a low or no correlation between toxicity and IBI. Even with low toxic environmental waters, toxicity test using 100-fold concentrated and medaka early fly could detect acute toxicity. The detected toxicity seemed to limit the inhabiting aquatic species in the water body.

INTRODUCTION: Arsenic (As) can be removed from water via rhizofiltration using phytostabilizing plants. The aim of this study was to investigate the performance of Eleocharis macrostachya in constructed wetland prototypes, as well as the plant's arsenic mass retention and the distribution of As along the wetland flow gradient and the soil in the wetland mesocosmos. MATERIALS AND METHODS: Experiments were carried out in laboratory-scale wetland prototypes, two planted with E. macrostachya and one without plants. Samples of water were taken at the inlet and outlet of the wetlands during the 33-week test period. At the end of the experiment, plants and soil (silty-sand) from each prototype were divided in three equal segments (entrance, middle and exit) and analyzed for their arsenic content. Results revealed that the planted wetlands have a higher As-mass retention capacity (87–90% of the total As inflow) than prototypes without plants (27%). RESULTS: As mass balance in the planted wetlands revealed that 78% of the total inflowing As was retained in the soil bed. Nearly 2% was absorbed in the plant roots, 11% was flushed as outflow, and the fate of the remaining 9% is unknown. In the prototype without plants, the soil retained 16% of As mass, 72% of the arsenic was accounted for in the outflow, and 12% was considered unknown. Although E. macrostachya retained only 2% of the total arsenic mass in their roots, its presence was a determining factor for arsenic retention in the wetland soil medium. CONCLUSION: Hence, planted wetlands might be a suitable option for treating As-contaminated water.

BACKGROUND: Cuttings and seedlings of Jatropha curcas L. were exposed to different regimes of lead (Pb) stress as Pb(NO3)2 at 0 (CK), 0.5, 1, 2, 3, and 4 mM kg−1 soil. OBJECTIVES: The effect of Pb treatment on the root length, tolerance index, photosynthetic pigments, photosynthetic activity, lipid peroxidation, and antioxidant enzyme was studied in a greenhouse pot experiment. RESULTS: The results showed that root lengths and tolerance index decreased with increase of Pb concentration, but tolerance index of cuttings was always lower than those of the seedlings. For cuttings, Pb treatment had a stimulating effect on chlorophyll content, carotenoid content, and superoxide dismutase (SOD) activity at low concentration and an inhibitory effect at higher concentration. For seedlings, SOD activity increased with increasing Pb concentration. In both seedlings and cuttings, Pb caused inhibition of leaf growth and photosynthesis, and induced the membrane damage which was more obvious in the cuttings. In comparison with the control, the dynamic tendency of catalase and perxidase activities in the leaves of Pb-stressed plants all ascended, and then declined. DISCUSSION: The increase in enzyme activities demonstrated that seedlings were more tolerant to Pb stress than cuttings. These results also indicate that the antioxidant system may play an important role in eliminating or alleviating the toxicity of Pb in J. curcas seedlings and cuttings. The accumulation of Pb increased in a concentration-dependent manner; however, its translocation from root to shoot was low. The cuttings accumulated significantly higher Pb in roots than seedlings.

INTRODUCTION: The unhairing step, a part of the beamhouse process, is particularly polluting, generating an alkaline wastewater with high concentrations of organic and inorganic matter. The aim of this study was to evaluate the treatment of this industrial wastewater using a combination of biological and microfiltration processes. MATERIALS AND METHODS: The performance of the activated sludge system (AS) was evaluated under varying organic loading rate (OLR) from 0.9 to 3.4 kg chemical oxygen demand (COD) m−3 day−1 and decreasing hydraulic retention time (HRT) from 3 to 1.6 days. RESULTS: For an HRT of 3 days, the increase of OLR significantly affected the removal of organic matter. Therefore, the biological organic matter removal of unhairing wastewater decreased from 92% to 66% for COD and from 87 to 53% for biological oxygen demand (BOD5). GC-MS analyses showed that biological treatment of unhairing wastewater contributed to the removal of long chain fatty acids and their degradation products. Microfiltration of unhairing wastewater was performed using 0.2 μm pore-size membranes in tangential filtration. The highest removal efficiencies were obtained for bacteria (100%) and turbidity (98.4%) which confirmed the importance of the microfiltration step in treatment of unhairing wastewater. The result showed that the flux decay rate was greatest at the start of the microfiltration assay (90 L h−1 m2), becoming 60.7 L h−1 m2 after 32 min. CONCLUSION: This change indicated that fouling occurred rapidly once the membrane module was put into operation.

PURPOSE: Resulting from their intensive use as corrosion inhibitors in aircraft deicing and anti-icing fluids (ADAF) and for silver protection in dishwasher detergents benzotriazoles (BTs) are widespread in European surface waters. The current study aimed on an ecotoxicological characterization of 1H-benzotriazole (1H-BT) and 5-methyl-1H-benzotriazole (5MBT). METHODS: Acute and chronic OECD guideline tests were conducted with primary producers (Desmodesmus subspicatus, Lemna minor) and two daphnia species (Daphnia magna, Daphnia galeata) to characterize the hazard of these chemicals. Additionally, the estrogenic activity of both BTs was analyzed in vitro using a recombinant yeast estrogen screen (YES). RESULTS: Both BTs revealed significant effects in acute and chronic experiments, but exhibited no estrogenic activity in the YES. The algal growth test displayed an inhibited cell number increase with effect concentration (EC) values of EC10 1.18 and 2.86 mg l-1 for 1H-BT and 5MBT, respectively. In the Lemna test, EC10 values were 3.94 mg l-1 (1H-BT) and 2.11 mg l-1 (5MBT). D. magna was also affected with EC50 (48 h) values of 107 mg l-1 for 1H-BT and 51.6 mg l-1 for 5MBT. D. galeata was more sensitive with an EC50 (48 h) of 14.7 mg 1H-BT l-1 and 8.13 mg 5MBT l-1. In the 21-day reproduction tests with D. magna, the EC10 for 5MBT was 5.93 mg l-1 while 1H-BT showed no adverse effects. D. galeata turned out to be more sensitive in the chronic study with EC10 values of 0.97 mg l-1 for 1H-BT and 0.40 mg l-1 for 5 MBT. CONCLUSION: Because BTs are regularly found in the aquatic environment at lower μg l-1 concentrations reflecting their persistence and poor elimination during wastewater treatment processes, a preliminary risk assessment was conducted. There is little indication that BTs pose a risk for aquatic ecosystems at current exposure levels during most of the year. However, it cannot be excluded that in winter with a higher usage of ADAFs environmental concentrations may well exceed the level that is considered safe for aquatic organisms.

Hexabromocyclododecanes (HBCDs), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), and decabromodiphenyl ethane (DBDPE) used as alternatives for polybrominated diphenyl ethers (PBDEs) are also persistent in the environment as PBDEs. Limited information on these non-PBDE brominated flame retardants (BFRs) is available; in particular, there are only few publications on environmental pollution by these contaminants in the coastal waters of Asia. In this regard, we investigated the contamination status of HBCDs, BTBPE, and DBDPE in the coastal waters of Asia using mussels as a bioindicator. Concentrations of HBCDs, BTBPE, and DBDPE were determined in green (Perna viridis) and blue mussels (Mytilus edulis) collected from the coastal areas in Cambodia, China (mainland), SAR China (Hong Kong), India, Indonesia, Japan, Malaysia, the Philippines, and Vietnam on 2003–2008. BTBPE and DBDPE were analyzed using GC-MS, whereas HBCDs were determined by LC-MS/MS. HBCDs, BTBPE, and DBDPE were found in mussels at levels ranging from <0.01 to 1,400, <0.1 to 13, and <0.3 to 22 ng/g lipid wt, respectively. Among the three HBCD diastereoisomers, α-HBCD was the dominant isomer followed by γ- and β-HBCDs. Concentrations of HBCDs and DBDPE in mussels from Japan and Korea were higher compared to those from the other Asian countries, indicating extensive usage of these non-PBDE BFRs in Japan and Korea. Higher levels of HBCDs and DBDPE than PBDEs were detected in some mussel samples from Japan. The results suggest that environmental pollution by non-PBDE BFRs, especially HBCDs in Japan, is ubiquitous. This study provides baseline information on the contamination status of these non-PBDE BFRs in the coastal waters of Asia.

Plant litter and organic sediments are a main sink for metals and metalloids in aquatic ecosystems. The effect of invertebrate shredder (a key species in litter decay) on metal/metalloid fixation by organic matter is described only under alkaline water conditions whereas for slightly acidic waters nothing can be found. Furthermore, less is known about the effect of invertebrate shredders on the quality of dissolved organic carbon (DOC) and nitrogen (DON) released during litter decay. We conducted an experiment to investigate the impact of invertebrate shredder (Gammarus pulex) on metal/metalloid fixation/remobilization and on the quality of DOC/DON released under slightly acidic water conditions. During decomposition of leaf litter, invertebrate shredder facilitated significantly the emergence of smaller particle sizes of organic matter. The capacity of metal fixation was significantly higher in smaller particles (POM 2,000–63 μm) compared to original leaf litter and litter residues. Thus, G. pulex enhanced metal fixation by organic partition of sediments by increasing the amount of smaller particle of organic matter in aquatic ecosystems. In contrast, the capacity of metal/metalloid fixation in the smallest fraction of POM (<63 μm) was lower compared with leaf residues in treatment without invertebrates. Remobilization of metals and metalloids was very low for all measured elements. A significant effect of invertebrates on quantitative formation of DOC/DON was confirmed. The quality of released DOC/DON, which may affect metal/metalloid remobilization, was also significantly affected by invertebrate shredders (e.g., more carboxylates). Hence, invertebrate shredder enhanced significantly the fixation of metals/metalloids into POM in slightly acidic environments.

INTRODUCTION: A synthetic water-soluble meso-tetra(2,6-dichloro-3-sulfonatophenyl)porphyrinate of iron(III) chloride, Fe-(TDCPPS)Cl, was employed to catalyze the oxidative co-polymerization of penta-halogenated phenols in two humic materials of different origin. MATERIALS AND METHODS: Co-polymerization of pentachlorophenol (PCP) was followed by high-performance size-exclusion chromatography (HPSEC), the unbound PCP recovered from reacting humic solutions was evaluated by gas-chromatography/electron capture detector, and the oxidative catalyzed coupling of pentafluorophenol (PFP) into humic matter was assessed by liquid-state 19F-NMR spectroscopy. HPSEC showed that the catalyzed oxidative coupling between PCP and humic molecules increased the apparent weight-average molecular weight (M w) values in both humic substances. RESULTS AND DISCUSSION: HPSEC further indicated that the co-polymerization reaction turned the loosely bound humic supramolecular structures into more stable conformations, which could no longer be disrupted by the disaggregating effect of acetic acid. The occurrence of covalent linkages established between PCP and humic molecules was also suggested by the very little amount of PCP found free in solution after the catalyzed co-polymerization. 19F-NMR spectroscopy suggested that also PFP could be oxidatively coupled to humic materials. PFP-humic co-polymerization reaction produced 19F-spectra with many more 19F signals and wider chemical shifts spread than for PFP alone or PFP subjected to catalyzed coupling without humic matter. CONCLUSIONS: These findings show that biomimetic iron-porphyrin is an efficient catalyst for the covalent binding of polyhalogenated phenols to humic molecules, thereby suggesting that the co-polymerization reaction may become a useful technology to remediate soils and waters contaminated by polyhalogenated phenols and their analogues.

BACKGROUND: The photocatalytic degradation of pyrene under UV (125 W Hg-Arc, 10.4 mW/cm2) irradiation of TiO2 aqueous suspension has been found to be highly improved with the dissolved transition metal ions like Cu2+, Fe3+, Ag+, and Au3+, etc. As the reduction potential of these metals lies below the conduction band (CB) position (−0.1 eV) of TiO2, the photoexcited electron transfer occurs more readily and reduces electron–hole recombination rate. Therefore, it has a beneficial influence on the photocatalytic ability of TiO2 because of rapid Fermi energy equilibrium between the CB of TiO2 and its surface adsorbed metal ions. RESULTS AND DISCUSSION: The Fermi level is referred to as the electrochemical potential and plays an important role in the band theory of solids. When metal and semiconductor are in contact, electron migration from photoirradiated semiconductor to the deposited metal occurs at the interface until two Fermi levels equilibrate and enhanced the photocatalytic activity of semiconductor photocatalyst. Ni2+ having more negative reduction potential (−0.25 eV) than the CB of TiO2 imparts negligible co-catalytic activity to TiO2 photoreaction. It also revealed that loading of Au3+ ions displayed higher degradation rate of pyrene than Au photodeposition. Furthermore, when the amount of dissolved Fe+3 and Au3+ ions gradually increases from 0.1 to 2 wt.%, the pyrene photodecomposition rate also become faster.