PURPOSE: The present study aims to investigate the individual and combined effects of temperature, pH, zero-valent bimetallic nanoparticles (ZVBMNPs) dose, and chloramphenicol (CP) concentration on the reductive degradation of CP using ZVBMNPs in aqueous medium. METHOD: Iron–silver ZVBMNPs were synthesized. Batch experimental data were generated using a four-factor statistical experimental design. CP reduction by ZVBMNPs was optimized using the response surface modeling (RSM) and artificial neural network-genetic algorithm (ANN-GA) approaches. The RSM and ANN methodologies were also compared for their predictive and generalization abilities using the same training and validation data set. Reductive by-products of CP were identified using liquid chromatography-mass spectrometry technique. RESULTS: The optimized process variables (RSM and ANN-GA approaches) yielded CP reduction capacity of 57.37 and 57.10 mg g−1, respectively, as compared to the experimental value of 54.0 mg g−1 with un-optimized variables. The ANN-GA and RSM methodologies yielded comparable results and helped to achieve a higher reduction (>6%) of CP by the ZVBMNPs as compared to the experimental value. The root mean squared error, relative standard error of prediction and correlation coefficient between the measured and model-predicted values of response variable were 1.34, 3.79, and 0.964 for RSM and 0.03, 0.07, and 0.999 for ANN models for the training and 1.39, 3.47, and 0.996 for RSM and 1.25, 3.11, and 0.990 for ANN models for the validation set. CONCLUSION: Predictive and generalization abilities of both the RSM and ANN models were comparable. The synthesized ZVBMNPs may be used for an efficient reductive removal of CP from the water.

BACKGROUND, AIM, AND SCOPE: Okadaic acid (OA) and analogues of dinophysistoxin (DTX) are key diarrheic shellfish poisoning (DSP) toxins, which possibly arouse DSP symptoms by consuming the contaminated shellfish. Because of the stable toxicity in high temperature and the long-term carcinogenicity, the outbreaks of DSP related to consumption of bivalve mollusks contaminated by DSP toxins pose a hazard to public health. Therefore, it is worth developing a fast and reliable analytical method for the detection of OA and analogues in shellfish. In this paper, an indirect competitive enzyme-linked immunosorbent assay (ELISA) (icELISA) for detecting OA and DTX-1 in seafood was developed based on monoclonal antibody (McAb). METHODS: The OA was conjugated to human immunoglobulin G (IgG) and bovine serum albumin (BSA) by the active ester method as the immune antigen and the detective antigen. The spleen cells from BALB/c mice immunized with OA-IgG were fused with SP2/0 myeloma cells. A hybridoma cell line, which secreted McAb against OA, was selected by “limiting dilution” cloning. An icELISA was developed based on immobilized conjugate (OA-BSA) competing the McAb with the free OA in seafood sample. RESULTS: A hybridoma cell line, which secreted IgG1 subclass monoclonal antibody (McAb) against OA, was selected. The IC₅₀ of the McAb for OA and dinophytoxin-1 (DTX-1) were 4.40 and 3.89 ng/mL, respectively. Based on the McAb, an indirect competitive ELISA for detection of OA and DTX-1 in seafood was developed. The regression equation was y = 54.713x − 25.879 with a coefficient correlation of R ² = 0.9729. The linear range and the limit of detection were 0.4–12.5 and 0.45 ng/mL, respectively. The average recovery of OA and DTX-1 spiked shellfish was 82.29% with the coefficient of variation of 7.67%. CONCLUSION: The developed icELISA is a fast, sensitive, and convenient assay for detecting of total amount of OA and DTX-1 in seafood.

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.

BACKGROUND: This study investigated the acute effect of benzo[a]anthracene, a significant compound among polycyclic aromatic hydrocarbons, on the biodegradation of a synthetic organic substrate—a peptone/meat extract mixture—under aerobic conditions. METHODS: A laboratory-scale sequencing batch reactor was sustained at steady state at a sludge age of 10 days with substrate feeding. Inhibition tests involved running a series of batch reactors initially seeded with the biomass obtained from the parent reactor. After the biomass seeding, the reactors were started with the peptone mixture and a range of initial benzo[a]anthracene concentrations between 0.5 and 88 mg/L. Experimental profiles of oxygen uptake rates and polyhydroxyalkanoates were evaluated by calibration of a selected model. RESULTS: Lower doses of benzo[a]anthracene had no effect on process kinetics. The noticeable acute impact was only observed with the addition of 88 mg/L of benzo[a]anthracene, but it was limited with the storage mechanism: the amount of organic substrate diverted to polyhydroxyalkanoates was significantly reduced with a corresponding decrease in the maximum storage rate, k STO, from 2.7 down to 0.6 day−1. Similarly, the maximum growth rate from internally stored polyhydroxyalkanoates was lowered from 2.3 to 1.0 day−1. CONCLUSION: Among the mechanisms for direct substrate utilization, only the hydrolysis rate was slightly reduced, but otherwise, the overall COD removal efficiency was not affected.

BACKGROUND, SCOPE, AND AIMS: Antibacterial fluoroquinolones (FQs) are third-generation antibiotics that are commonly used as therapeutic treatments of respiratory and urinary tract infections. They are used far less in intensively farmed animal production systems, though their use may be permitted in the veterinary treatments of flocks or in medicated feeds. When used, only a fraction of ingested parent FQ actually reaches the in vivo target site of infection, while the remainder is excreted as the parent FQ and its metabolized products. In many species’ metabolism, enrofloxacin (EF) is converted into ciprofloxacin (CF) while both FQs are classified as parent FQs in human treatments. It is therefore likely that both FQs and their metabolic products will contribute to a common pool of metabolites in biological wastes. Wastes from intensive farming practices are either directly applied to agricultural land without treatment or may be temporarily stored prior to disposal. However, human waste is treated in sewage treatment plants (STPs) where it is converted into biosolids. In the storage or treatment process of STPs, FQs and their in vivo metabolites are further converted into other environmental metabolites (FQEMs) by ex vivo physicochemical processes that act and interact to produce complex mixtures of FQEMs, some of which have antibacterial-like activities. Biosolids are then often applied to agricultural land as a fertilizer amendment where FQs and FQEMs can be further converted into additional FQEMs by soil processes. It is therefore likely that FQ-contaminated biowaste-treated soils will contain complex mixtures of FQEMs, some of which may have antibacterial-like activities that may be expressed on bacteria endemic to the receiving agricultural soil environment. Concern has arisen in the scientific and in the general community that repeated use of FQ-contaminated biowaste as fertilizer amendments of nutrient-impoverished agricultural land may create a selective environment in which FQ-resistant bacteria might grow. The likelihood of this happening will depend, to some extent, on whether bioactive FQEMs are first synthesized from the parent FQs by the action and interaction of in vivo and ex vivo processes producing bioactive FQEMs in biowastes and biosolids. The postulated creation of a selective environment will also depend, in part, on whether such bioactive FQEMs are biologically available to bacteria, which may, in turn, be influenced by soil type, amendment regime, and the persistence of the bioactive FQEMs. Additionally, soil bacteria and soil processes may be affected in different ways or extents by bioactive FQEMs that could possibly act additively or synergistically at ecological targets in these non-target bacteria. This is an important consideration, since, while parent FQs have well-defined ecological targets (DNA gyrase and topoisomerase IV) and modes of bactericidal action, the FQEMs and their possible modes of action on the many different species of soil bacteria is less well studied. It is therefore understandable that there is a lack of conclusive evidence directly attributing biosolid usage to any increase in FQ-resistant bacteria detected in biowaste-amended agricultural soil. However, a lack of evidence may simply imply that a causal relationship between biosolid usage programs and any detection of low levels of FQ-resistant bacteria in soils has yet to be established, rather than an assumption of no relationship whatsoever. Based on results presented in this paper, the precautionary principle should be applied in the usage of FQ-contaminated biosolids as fertilizer amendments of agricultural land. The aim of this research was to test whether any bioactive FQEMs of EF could be synthesized by aerobic fermentation processes using Mycobacterium gilvum (American Tissue Culture Collection) and a mixed culture of microorganisms derived from an agricultural soil. High-performance thin-layer chromatography (HPTLC) and bioautography were tested as screening techniques in the detection and analysis of bioactive FQEMs. MATERIALS AND METHODS: FQEMs derived from M. gilvum and mixed (soil) culture aerobic ferments were fractionated using preparative HPTLC. A standard strain of Escherichia coli was then used as the reporter organism in a bioautography assay in the detection of bioactive-FQEMs on a mid-section of the HPTLC plate. Plate sections were reassembled, and a photograph was taken under low-intensity ultraviolet (UV) light to reveal regions that contained analytes that had UV chromophores and antibacterial-like activities. RESULTS AND DISCUSSION: Many fractionated FQEMs displayed antibacterial-like activity while bound to silica gel HPTLC plates. These results also provide evidence that sufficient quantities of biologically active FQEMs were biologically available from a silica gel surface to prevent the adherent growth of E. coli. Six to seven FQEMs derived from EF using aerobic fermentation processes had antibacterial-like activities, while two FQEMs were also detectable using UV light. Furthermore, similar banding patterns of antibacterial-like activity were observed in both the monoculture (M. gilvum) and mixed culture bioautography assays, indicating that similar processes operated in both aerobic fermentations, either producing similar biologically active FQEMs or biologically active FQEMs that had similar physicochemical properties in both ferments. The simplest explanation for these findings is that the tested agricultural soil also contained mycobacteria that metabolized EF in a similar way to the purchased standard monoculture M. gilvum. Additionally, the marked contrast between the bioautography results and the UV results indicated that the presence of UV chromophores is not a prerequisite for the detection of antibacterial-like activity. CONCLUSIONS: A reliance on spectrophotometric techniques in the detection of bioactive FQEMs in the environment may underestimate component antibacterial-like activity and, possibly, total antibacterial-like activity expressed by EF and its FQEMs. The described bioautography method provides a screening technique with which antibacterial-like activities derived from EF and possibly other FQs can be detected directly on silica gel HPTLC plates. RECOMMENDATIONS: It is recommended that both bioassay and instrumental analytical techniques be used in any measurement of hazard and risk relating to antibacterial-like activities in the environment that are derived from fluoroquinolone antibiotics and their environmental metabolites.

Over the past decade, several studies have reported trace levels of endocrine disrupting compounds, pharmaceuticals, and personal care products in surface waters, drinking water, and wastewater effluents. There has also been an increased concern about the ecological and human health impact of these contaminants, and their removal from water and wastewater has become a priority. Traditional treatment processes are limited in their ability to remove emerging contaminants from water, and there is a need for new technologies that are effective and feasible. This paper presents a review on recent research results on molecularly imprinted (MIP) and non-imprinted (NIP) polymers and evaluates their potential as a treatment method for the removal of emerging contaminants from water and wastewater. It also discusses the relative benefits and limitations of using MIP or NIP for water and wastewater treatment. MIP, and in particular NIP, offer promising applications for wastewater treatment, but their toxicity and possible health effects should be carefully studied before they are considered for drinking water treatment. More research is also required to determine how best to incorporate MIP and NIP in treatment plants.

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.

BACKGROUND, AIM, AND SCOPE: This study demonstrated the adsorption capacity of microcystin-LR (MC-LR) onto sediment samples collected from different reservoirs (Emerald and Jade reservoirs) and rivers (Dongshan, Erhjen, and Wukai rivers) in Taiwan to investigate the fate, transport behavior, and photodegradation of MC-LR. MAIN FEATURES: Langmuir adsorption and photodegradation studies were carried out in the laboratory and tested the capability of sediments for MC-LR adsorption. These data suggested that sediments play a crucial role in microcystins degradation in aquatic systems. RESULTS AND DISCUSSION: The results of batch experiments revealed that the adsorption of MC-LR varied significantly with texture, pH, and organic matter content of sediments. Silty and clay textures of the samples were associated with larger content of organic matter, and they displayed the enhanced MC-LR adsorption. Low pH sediment showed increased adsorption of MC-LR. The effective photodegradation of MC-LR (1.6 μg/mL) was achieved within 60 min under 254 nm light irradiation. CONCLUSION: A comparative study of adsorption capacity of all sediment samples was carried out and discussed with respect to different aspects. Among all, sediments collected from Jade reservoir showed enhanced MC-LR adsorption (11.86 μg/g) due to favored textural properties (BET surface area = 20.24 m2/g and pore volume = 80.70 nm). PERSPECTIVES: These data provide important information that may be applied to management strategies for improvement of water quality in reservoirs and rivers and other water bodies in Taiwan.

PURPOSE: An online cloud-point extraction (CPE) coupled with flow injection method is developed for the separation and preconcentration of palladium and lead from various matrices using flame atomic absorption spectrometry (FAAS). METHOD: The method employs the formation of complexes of the metallic species with dimethylglyoxime, which are subsequently entrapped in the micelles of the surfactant Triton X-114, upon increase of the solution temperature to 60°C and loaded into the flow injection system at a flow rate of 4.6 mL min−1. The surfactant rich-phase was retained in a minicolumn packed with animal wool at pH 6 and eluted with 1.0 mol L−1 nitric acid in methanol at a flow rate of 1.1 mL min−1 directly into the nebulizer of the FAAS. The CPE variables and flow injection conditions affecting the analytical performance of the combined methodology was studied and optimized. RESULTS: Under the optimized conditions for 25 mL of preconcentrated solution, the enrichment factors were 51 and 44, and the limit of detections were 1.0 and 1.4 ng mL−1 for palladium and lead, respectively. Finally, the developed method was applied for the determination of palladium and lead in street dust, soil, radiology waste, catalytic converter, and urban aerosol samples. CONCLUSIONS: Cloud-point extraction coupled with flow injection-FAAS was proposed as an effective preconcentration and separation method for Pd and Pb determination in radiology waste, road dust, soil, and urban aerosol samples. The most favorable feature of this method is its much higher selectivity, sensitivity, rapidity, good extraction efficiency, and employs the green chemistry concept, as it does not require the addition of toxic chemicals. In addition, this proposed method gives very low detection limits and good relative standard.

PURPOSE: A multiple inputs and multiple outputs (MIMO) fuzzy-logic-based model was proposed to estimate color and chemical oxygen demand (COD) removal efficiencies in the post-treatment of anaerobically pretreated poultry manure wastewater effluent using Fenton's oxidation process. Three main input variables including initial pH, Fe+2, and H2O2 dosages were fuzzified in a new numerical modeling scheme by the use of an artificial intelligence-based approach. MATERIALS AND METHODS: Trapezoidal membership functions with eight levels were conducted for the fuzzy subsets, and a Mamdani-type fuzzy inference system was used to implement a total of 70 rules in the IF–THEN format. The product (prod) and the center of gravity (centroid) methods were applied as the inference operator and defuzzification methods, respectively. Fuzzy-logic predicted results were compared with the outputs of two first-order polynomial regression models derived in the scope of this study. Estimated results were also compared to the multiple regression approach by means of various descriptive statistical indicators, such as root mean-squared error, index of agreement, fractional variance, proportion of systematic error, etc. RESULTS AND DISCUSSION: Results of the statistical analysis clearly revealed that, compared to conventional regression models, the proposed MIMO fuzzy-logic model produced very smaller deviations and demonstrated a superior predictive performance on forecasting of color and COD removal efficiencies with satisfactory determination coefficients over 0.98. CONCLUSIONS: Due to high capability of the fuzzy-logic methodology in capturing the non-linear interactions, it was demonstrated that a complex dynamic system, such as Fenton's oxidation, could be easily modeled.