Bacterial assisted phytoremediation for enhanced degradation of highly sulfonated diazo reactive dye

Purpose

Phytoremediation is the exploitation of plants and their rhizospheric microorganisms for pollutants treatment like textile dyes, which are toxic, carcinogenic and mutagenic from the effluent. The purpose of this work was to explore a naturally found plant and bacterial synergism to achieve an enhanced degradation of Remazol Black B dye (RBB).

Methods

In vitro cultures of Zinnia angustifolia were obtained by seed culture method. Enzymatic analysis of the plant roots and Exiguobacterium aestuarii strain ZaK cells was performed before and after decolorization of RBB. Metabolites of RBB formed after its degradation were analyzed using UV?CVis spectroscopy, high-performance liquid chromatography (HPLC), Fourier transform infrared (FTIR) and gas chromatography?Cmass spectrometry (GC-MS). Phytotoxicity studies were performed.

Results

The consortium ZE was found to be more efficient than individual plant and bacteria. Z. angustifolia roots showed significant induction in the activities of lignin peroxidase, laccase, DCIP reductase and tyrosinase during dye decolorization. E. aestuarii showed significant induction in the activities of veratryl alcohol oxidase, azo reductase and DCIP reductase. Analysis of metabolites revealed differential metabolism of RBB by plant, bacteria and consortium ZE. E. aestuarii and Z. angustifolia led to the formation of 3,6-diamino-4-hydroxynaphthalene-2-sulfonic acid, (ethylsulfonyl)benzene, and 3,4,6-trihydroxynaphthalene-2-sulfonic acid and propane-1-sulfonic acid, respectively, whereas consortium ZE produced 4-hydroxynaphthalene-2-sulfonic acid, naphthalene-2-sulfonic acid and 4-(methylsulfonyl)phenol. The phytotoxicity study revealed the nontoxic nature of the metabolites formed after dye degradation.

Conclusion

Consortium ZE was found to be more efficient and faster in the degradation of RBB when compared to degradation by Z. angustifoila and E. aestuarii individually.     

Application of central composite face-centered design and response surface methodology for the optimization of electro-Fenton decolorization of Azure B dye

Purpose

The aim of this work was to improve the ability of electro-Fenton technique for the remediation of wastewater contaminated with synthetic dyes using a model azo dye such as Azure B.

Methods

Batch experiments were conducted to study the effects of main parameters, such as dye concentration, electrode surface area, treatment time, and voltage. In this study, central composite face-centered experimental design matrix and response surface methodology were applied to design the experiments and evaluate the interactive effects of the four studied parameters. A total of 30 experimental runs were set, and the kinetic data were analyzed using first- and second-order models.

Results

The experimental data fitted to the empirical second-order model of a suitable degree for the maximum decolorization of Azure B by electro-Fenton treatment. ANOVA analysis showed high coefficient of determination value (R ²?=?0.9835) and reasonable second-order regression prediction. Pareto analysis suggests that the variables, time, and voltage produce the largest effect on the decolorization rate.

Conclusion

Optimum conditions suggested by the second-order polynomial regression model for attaining maximum decolorization were dye concentration 4.83?mg/L, electrode surface area 15?cm², voltage 14.19?V, and treatment time of 34.58?min.     

Highly efficient decolorization of Malachite Green by a novel Micrococcus sp. strain BD15

Purpose

Malachite Green (MG) is used for a variety of applications but is also known to be carcinogenic and mutagenic. In this study, a novel Micrococcus sp. (strain BD15) was observed to efficiently decolorize MG. The purposes of this study were to explore the optimal conditions for decolorization and to evaluate the potential use of this strain for MG decolorization.

Methods

Optical microscope and UV?Cvisible analyses were carried out to determine whether the decolorization was due to biosorption or biodegradation. A Plackett?CBurman design was employed to investigate the effect of various parameters on decolorization, and response surface methodology was then used to explore the optimal decolorization conditions. Kinetics analysis and antimicrobial activity tests were also performed.

Results

The results indicated that the decolorization by the strain was mainly due to biodegradation. Concentrations of MG, urea, and yeast extract and inoculum size had significantly positive effects on MG decolorization, while concentrations of CuCl₂ and MgCl₂, and temperature had significantly negative effects. The interaction between different parameters could significantly affect decolorization, and the optimal conditions for decolorization were 1.0 g/L urea, 0.9 g/L yeast extract, 100 mg/L MG, 0.1 g/L inoculums (dry weight), and incubation at 25.2°C. Under the optimal conditions, 96.9% of MG was removed by the strain within 1 h, which represents highly efficient microbial decolorization. Moreover, the kinetic data for decolorization fit a second-order model well, and the strain showed a good MG detoxification capability.

Conclusion

Based on the results of this study, we propose Micrococcus sp. strain BD15 as an excellent candidate strain for MG removal from wastewater.     

Bioremediation of chromium by novel strains Enterobacter aerogenes T2 and Acinetobacter sp. PD 12 S2

Purpose

This study had an objective to identify the most potent chromium-resistant bacteria isolated from tannery effluent and apply them for bioremediation of chromium in tannery effluents.

Methods

Two such strains (previously characterized and identified by us)??Enterobacter aerogenes (NCBI GenBank USA Accession no. GU265554) and Acinetobacter sp. PD 12 (NCBI GenBank USA Accession no. GU084179)??showed powerful chromium resistivity and bioremediation capabilities among many stains isolated from tannery waste. Parameters such as pH, concentration of hexavalent chromium or Cr (VI), and inoculum volume were varied to observe optimum bioconversion and bioaccumulation of Cr (VI) when the said strains were grown in M9 minimal salt media. E. aerogenes was used to remediate chromium from tannery effluents in a laboratory level experiment.

Results

Observation by Scanning Electron Microscope and chromium peak in Energy Dispersive X-ray Spectroscopic microanalysis revealed that E. aerogenes helped remediate a moderate amount of Cr (VI) (8?C16?mg?L^?1) over a wide range of pH values at 35?C37°C (within 26.05?h). High inoculum percentage of Acinetobacter sp. PD 12 also enabled bioremediation of 8?C16?mg?L^?1 of Cr (VI) over a wide range of temperature (25?C37°C), mainly at pH?7 (within 63.28?h). The experiment with real tannery effluent gave very encouraging results.

Conclusion

The strain E. aerogenes can be used in bioremediation of Cr (VI) since it could work in actual environmental conditions with extraordinarily high capacity.     

Enhanced degradation of azo dye alizarin yellow R in a combined process of iron–carbon microelectrolysis and aerobic bio-contact oxidation

Purpose

With the aim of enhanced degradation of azo dye alizarin yellow R (AY) and further removal of the low-strength recalcitrant matter (LsRM) of the secondary effluent as much as possible, our research focused on the combination of aerobic bio-contact oxidation (ABO) with iron/carbon microelectrolysis (ICME) process.

Materials and methods

The combined ABO (with effective volume of 2.4?l) and ICME (with effectively volume of 0.4?l) process were studied with relatively short hydraulic retention time (HRT) of 4 or 6?h.

Results

At the HRT of 6?h with the reflux ratio of 1 and 2, the AY degradation efficiency in the final effluent was >96.5%, and the total organic carbon (TOC) removal efficiency were 69.86% and 79.44%, respectively. At the HRT of 4?h and the reflux ratio of 2, TOC removal efficiency and AY degradation efficiency were 73.94% and 94.89%, respectively. The ICME process obviously enhanced the total AY removal and the generated micromolecule acids and aldehydes then that wastewater backflow to the ABO where they were further biodegraded.

Conclusion

The present research might provide the potential options for the advanced treatment azo dyes wastewater with short HRT and acceptable running costs.     

Acid violet 7 and its biodegradation products induce chromosome aberrations,lipid peroxidation,and cholinesterase inhibition in mouse bone marrow

Introduction  

Acid violet 7 (AV7), mostly used in food, paper, cosmetic, and especially in textile industries, was degraded by Pseudomonas putida mt-2 at concentrations up to 200 mg/l.     

Isolation and characterization of Bacillus cereus IST105 from electroplating effluent for detoxification of hexavalent chromium

Purpose

Electroplating industries are the main sources of heavy metals, chromium, nickel, lead, zinc, cadmium and copper. The highest concentrations of chromium (VI) in the effluent cause a direct hazards to human and animals. Therefore, there is a need of an effective and affordable biotechnological solution for removal of chromium from electroplating effluent.

Methods

Bacterial strains were isolated from electroplating effluent to find out higher tolerant isolate against chromate. The isolate was identified by 16S rDNA sequence analysis. Absorbed chromium level of bacterium was determined by inductively coupled plasma-atomic emission spectrometer (ICP-AES), atomic absorption spectrophotometer (AAS), scanning electron microscope (SEM), transmission electron microscope (TEM) and energy dispersive X-ray analysis (EDX). Removal of metals by bacterium from the electroplating effluent eventually led to the detoxification of effluent confirmed by MTT assay. Conformational changes of functional groups of bacterial cell surface were studied through Fourier transform infrared spectroscopy.

Results

The chromate tolerant isolate was identified as Bacillus cereus. Bacterium has potency to remove more than 75% of chromium as measured by ICP-AES and AAS. The study indicated the accumulation of chromium (VI) on bacterial cell surface which was confirmed by the SEM-EDX and TEM analysis. The biosorption of metals from the electroplating effluent eventually led to the detoxification of effluent. The increased survivability of Huh7 cells cultured with treated effluent also confirmed the detoxification as examined by MTT assay.

Conclusion

Isolated strain B. cereus was able to remove and detoxify chromium (VI). It would be an efficient tool of the biotechnological approach in mitigating the heavy metal pollutants.     

Inactivation of bacteria under visible light and in the dark by Cu films. Advantages of Cu-HIPIMS-sputtered films

Introduction

The Cu polyester thin-sputtered layers on textile fabrics show an acceptable bacterial inactivation kinetics using sputtering methods.

Materials and methods

Direct current magnetron sputtering (DCMS) for 40?s of Cu on cotton inactivated Escherichia coli within 30?min under visible light and within 120?min in the dark. For a longer DCMS time of 180?s, the Cu content was 0.294% w/w, but the bacterial inactivation kinetics under light was observed within 30?min, as was the case for the 40-s sputtered sample.

Results and discussion

This observation suggests that Cu ionic species play a key role in the E. coli inactivation and these species were further identified by X-ray photoelectron spectroscopy (XPS). The 40-s sputtered samples present the highest amount of Cu sites held in exposed positions interacting on the cotton with E. coli. Cu DC magnetron sputtering leads to thin metallic semi-transparent gray?Cbrown Cu coating composed by Cu nanoparticulate in the nanometer range as found by electron microscopy (EM). Cu cotton fabrics were also functionalized by bipolar asymmetric DCMSP.

Conclusion

Sputtering by DCMS and DCMSP for longer times lead to darker and more compact Cu films as detected by diffuse reflectance spectroscopy and EM. Cu is deposited on the polyester in the form of Cu₂O and CuO as quantified by XPS. The redox interfacial reactions during bacterial inactivation involve changes in the Cu oxidation states and in the oxidation intermediates and were followed by XPS. High-power impulse magnetron sputtering (HIPIMS)-sputtered films show a low rugosity indicating that the texture of the Cu nanoparticulate films were smooth. The values of R _q and R _a were similar before and after the E. coli inactivation providing evidence for the stability of the HIPIMS-deposited Cu films. The Cu loading percentage required in the Cu films sputtered by HIPIMS to inactivate E. coli was about three times lower compared to DCMS films. This indicates a substantial Cu metal savings within the preparation of antibacterial films.     

An investigation of anthraquinone dye biodegradation by immobilized Aspergillus flavus in fluidized bed bioreactor

Purpose

Biodegradation and biodecolorization of Drimarene blue K₂RL (anthraquinone) dye by a fungal isolate Aspergillus flavus SA2 was studied in lab-scale immobilized fluidized bed bioreactor (FBR) system.

Method

Fungus was immobilized on 0.2-mm sand particles. The reactor operation was carried out at room temperature and pH?5.0 in continuous flow mode with increasing concentrations (50, 100, 150, 200, 300, 500?mg?l^?1) of dye in simulated textile effluent on the 1st, 2nd, 5th, 8th, 11th, and 14th days. The reactors were run on fill, react, settle, and draw mode, with hydraulic retention time (HRT) of 24?C72?h. Total run time for reactor operation was 17?days.

Results

The average overall biological oxygen demand (BOD), chemical oxygen demand (COD), and color removal in the FBR system were up to 85.57%, 84.70%, and 71.3%, respectively, with 50-mg?l^?1 initial dye concentration and HRT of 24?h. Reductions in BOD and COD levels along with color removal proved that the mechanism of biodecolorization and biodegradation occurred simultaneously. HPLC and LC?CMS analysis identified phthalic acid, benzoic acid, 1, 4-dihydroxyanthraquinone, 2,3-dihydro-9,10-dihydroxy-1,4-anthracenedione, and catechol as degradation products of Drimarene blue K₂RL dye. Phytotoxicity analysis of bioreactor treatments provided evidence for the production of less toxic metabolites in comparison to the parent dye.

Conclusion

The present fluidized bed bioreactor setup with indigenously isolated fungal strain in its immobilized form is efficiently able to convert the parent toxic dye into less toxic by-products.     

Blooming of Microcystis aeruginosa in the reservoir of the reclaimed land and discharge of microcystins to Isahaya Bay (Japan)

Purpose

In the reservoir created in the reclaimed land in Isahaya Bay, Japan, Microcystis aeruginosa, which produces microcystins (MCs), bloomed every year, and the water with high levels of MCs in the reservoir has been often drained to Isahaya Bay to adjust the water level. The principal aims of this study are to clarify the water conditions suitable for blooming of M. aeruginosa in the reservoir, to follow the amount of distribution of MCs inside and outside the reservoir, and to discuss how blooming of M. aeruginosa is controlled in the reservoir and how MCs produced by Microcystis spread or accumulate in the aquatic environment.

Method

We monitored the water quality (temperature, salinity, dissolved inorganic nitrogen (DIN), and dissolved inorganic phosphorus) in the reservoir with seasonal blooming of microalgae including phytoplankton and M. aeruginosa using the concentrations of chlorophyll ?? and MCs, respectively, and collected the surface sediment in the reservoir and the bay to determine the MC content using the ELISA method.

Result

M. aeruginosa bloomed in extremely low DIN conditions of the water in warm seasons (spring and late summer to autumn). The year-mean standing stock of MCs was approximately 34.5?kg in the water and 8.4?kg in the surface sediment in the reservoir. Approximately 64.5?kg of MCs was discharged with the effluent to the bay in a year.

Conclusion

Since a large amount of MCs always suspends in the water in the reservoir and it has been discharged to the bay, suspension-feeding animals are exposed most seriously to the high levels of MCs occurring in these areas. We need to pay attention to the danger of widespread dispersal of MCs and biological concentration of MCs by fish and clam inside and outside the reservoir.     

Removal of faecal indicator pathogens from waters and wastewaters by photoelectrocatalytic oxidation on TiO2/Ti films under simulated solar radiation

Purpose

The disinfection efficiency of water and secondary treated wastewater by means of photoelectrocatalytic oxidation (PEC) using reference strains of Enterococcus faecalis and Escherichia coli as faecal indicators was evaluated. Operating parameters such as applied potential (2?C10?V), initial bacterial concentration (10³?C10⁷?CFU/mL), treatment time (up to 90?min) and aqueous matrix (pure water and treated effluent) were assessed concerning their impact on disinfection.

Methods

PEC experiments were carried out using a TiO₂/Ti film anode and a zirconium cathode in the presence of simulated solar radiation. Bacterial inactivation was monitored by the culture method and real-time SYBR green PCR.

Results

A 6.2 log reduction in E. faecalis population was achieved after 15?min of PEC treatment in water at 10?V of applied potential and an initial concentration of 10⁷?CFU/mL; pure photocatalysis (PC) led to only about 4.3 log reduction, whilst negligible inactivation was recorded when the respective electrochemical oxidation process was applied (i.e. without radiation). PEC efficiency was generally improved increasing the applied potential and decreasing initial bacterial concentration. Regarding real wastewater, E. coli was more susceptible than E. faecalis during treatment at a potential of 5?V. Wastewater disinfection was affected by its complex composition and the contained mixed bacterial populations, yielding lower inactivation rates compared to water treatment. Screening the results obtained from both applied techniques (culture method and real-time PCR), there was a discrepancy regarding the recorded time periods of total bacterial inactivation, with qPCR revealing longer periods for complete bacterial reduction.

Conclusions

PEC is superior to PC in terms of E. faecalis inactivation presumably due to a more efficient separation and utilization of the photogenerated charge carriers, and it is mainly affected by the applied potential, initial bacterial concentration and the aqueous matrix.     

Aquatic ecotoxicity assessment of a new natural formicide

Background, aim and scope

Agrochemicals could reach aquatic ecosystems and damage ecosystem functionality. Natural formicide could be an alternative to use in comparison with the more toxic formicides available on the market. Thus, the objective of this study was to assess the ecotoxicity of the new natural formicide Macex? with a battery of classical aquatic ecotoxicity tests.

Material and methods

Bacteria (Aliivibrio fischeri), algae (Pseudokirchneriella subcapitata), hydra (Hydra attenuata), daphnids (Daphnia magna), and fish (Danio rerio) tests were performed in accordance with international standardized methodologies.

Results

In the range of formicide concentrations tested (0.03 to 2.0?g?L^?1) EC₅₀ values varied from 0.49 to >2.0?g?L^?1, with P. subcapitata being the most sensitive species and H. attenuata and D. rerio the most tolerant species to this product in aqueous solutions.

Conclusions

This new formicide preparation can be classed as a product of low toxicity compared to the aquatic ecotoxicity of the most common commercialized formicides.     

Evaluation of substrate removal kinetics for UASB reactors treating chlorinated ethanes

Purpose

Lack of focus on the treatment of wastewaters bearing potentially hazardous pollutants like 1,1,2 trichloroethane and 1,1,2,2 tetrachloroethane in anaerobic reactors has provided an impetus to undertake this study. The objective of this exercise was to quantify the behavior of upflow anaerobic sludge blanket reactors and predict their performance based on the overall organic substrate removal.

Methods

The reactors (wastewater-bearing TCA (R2), and wastewater-bearing TeCA (R3)) were operated at different hydraulic retention times (HRTs), i.e., 36, 30, 24, 18, and 12?h corresponding to food-to-mass ratios varying in the range of 0.2?C0.7?mg chemical oxygen demand (COD) mg^?1 volatile suspended solids day^?1. The process kinetics of substrate utilization was evaluated on the basis of experimental results, by applying three mathematical models namely first order, Grau second order, and Michaelis-Menten type kinetics.

Results

The results showed that the lowering of HRT below 24?h resulted in reduced COD removal efficiencies and higher effluent pollutant concentrations in the reactors. The Grau second-order model was successfully applied to obtain the substrate utilization kinetics with high value of R ² (>0.95). The Grau second-order substrate removal constant (K ₂) was calculated as 1.12 and 7.53?day^?1 for reactors R2 and R3, respectively.

Conclusion

This study demonstrated the suitability of Grau second-order kinetic model over other models, for predicting the performance of reactors R2 and R3, in treating wastewaters containing chlorinated ethanes under different organic and hydraulic loading conditions.     

Arsenic accumulation and speciation in the submerged macrophyte Ceratophyllum demersum L.

Introduction

Ceratophyllum demersum L. is a widespread submerged macrophyte in aquatic environments.

Methods

Simulation experiments were conducted in the laboratory to investigate arsenic (As) accumulation, speciation, and efflux of C. demersum exposed to arsenate and arsenite solutions.

Results

Plant shoots showed a significant accumulation of As with a maximum of 862 and 963???g?As?g^?1 dry weight after 4?days of exposure to 10???M arsenate and arsenite, respectively. Regardless of whether arsenate or arsenite was supplied to the plants, arsenite was the predominant species in plant shoots. Furthermore, a dramatically higher influx rate of arsenate compared with arsenite was observed in C. demersum exposed to As solutions without the addition of phosphate (P). Arsenate uptake was considerably inhibited by P in this study, suggesting that arsenate is taken up by C. demersum via the phosphate transporters. However, arsenite uptake was unaffected by P and markedly reduced in the presence of glycerol and antimonite (Sb), indicating arsenite shares the aquaporin transport pathway. In addition, C. demersum rapidly reduces arsenate to arsenite in the shoot of the plant and extrudes most of them (>60?%) to the external solutions. The efflux of arsenite was much higher than that of arsenate; the former is supposed to be both active and passive processes, and the latter through passive leakage.

Conclusion

C. demersum is a strong As accumulator and an interesting model plant to study As uptake and metabolism due to the lack of a root-to-shoot translocation barrier.     

Efficient biosorption of chromium(VI) ion by dry Araucaria leaves

Background

In this paper, batch removal of hexavalent chromium from aqueous solutions by Araucaria heterophylla leaves was investigated. The batch experiments were conducted to study the adsorption of metal species and effect of different pH, contact time, metal concentration, biosorbent concentration, and adsorption capacity.

Method

Freundlich and Langmuir??s isotherm model were used to describe the adsorption behavior, and the experimental results fitted Freundlich model well.

Results

The adsorption efficiency observed for all chromium concentrations, i.e., 1, 3, 5, and 10?mg/L was 100% and the equilibrium was achieved in 30?min for 1 and 3?mg/L, whereas for 5 and 10?mg/L, it was less than 60?min. FTIR spectra was taken to identify functional groups involved in the biosorption.

Conclusion

Thus, Araucaria leaves can be considered as one of the cheap and efficient biosorbent for toxic hexavalent chromium removal from natural or wastewaters.     

Changes in character of organics in the receiving environment of effluent from a sulphite pulp mill

Purpose

The characteristics of organics in sulphite pulp mill effluent and in the receiving environment of effluent discharge were investigated to assess the basis for the persistence or attenuation of colour.

Methods

Characterization of organics was conducted through determination of SUVA, specific colour, and molecular weight distribution of organics using high performance size exclusion chromatography and by solid-state ¹³?C cross polarization (CP) NMR. The characteristics of organics from mill wastewater before and after secondary aerobic treatment, followed by lime treatment and from the receiving environment, an enclosed brackish lake were compared. Changes in the character of organics in lake water over a period of 14?years were studied in the context of changes in mill processing and climate impacts.

Results

High colour in mill effluent and in receiving waters correlated with high SUVA and specific colour levels, high molecular weight range and aromatic content. Conversely, lake waters with low colour had UV absorbing compounds of much lower molecular weight range and low relative abundance of aromatic compounds. Attenuation of colour and changes in the character of organics in the receiving environment coincided with increased concentrations of metal cations.

Conclusions

These increased concentrations appear to be due to the effects of climate change, lake management and their presence in mill effluent, with subsequent discharge to the lake. Attenuation of colour was found to be predominantly through removal of high molecular weight aromatic compounds where the removal processes could be through adsorption and co-precipitation with divalent metals, as well as through dilution processes.     

Increased urinary 8-hydroxy-2��-deoxyguanosine levels in workers exposed to di-(2-ethylhexyl) phthalate in a waste plastic recycling site in China

Background

Di-(2-ethylhexyl) phthalate (DEHP) is a common plasticizer used in industrial and diverse consumer products. Animal studies indicate DEHP caused developmental, reproductive, and hepatic toxicities. However, human studies of the potential effects of DEHP are limited.

Methods

The exposed site with a history of over 20 years of waste plastic recycling was located in Hunan Province, China. The reference site without known DEHP pollution source was about 50 km far away from the exposed site. In this study, 181 workers working in plastic waste recycling and 160 gender?Cage matched farmers were recruited. DEHP concentrations in water and cultivated soil samples, serum thyroid-stimulating hormone, malondialdehyde (MDA), superoxide dismutase (SOD), urinary 8-hydroxy-2??-deoxyguanosine (8-OHdG), and micronuclei frequency in human capillary blood lymphocytes were analyzed.

Results

Mean levels of DEHP were greater in environment at the recycling site than at reference site (industry wastewater for the exposed: 42.43 ??g/l; well water: 14.20 vs. 0.79 ??g/l, pond water: 135.68 vs. 0.37 ??g/l, cultivated soil: 13.07 vs. 0.81 mg/kg, p?p?p?Conclusions The occupational DEHP exposure might contribute to oxidative deoxyribonucleic acid damage in the male workers.     

Biosorption of Cr(VI) by free and immobilized Pediastrum boryanum biomass: equilibrium, kinetic, and thermodynamic studies

Background and purpose

The biosorption of Cr(VI) from aqueous solution has been studied using free and immobilized Pediastrum boryanum cells in a batch system. The algal cells were immobilized in alginate and alginate?Cgelatin beads via entrapment, and their algal cell free counterparts were used as control systems during biosorption studies of Cr(VI).

Methods

The changes in the functional groups of the biosorbents formulations were confirmed by Fourier transform infrared spectra. The effect of pH, equilibrium time, initial concentration of metal ions, and temperature on the biosorption of Cr(VI) ion was investigated.

Results

The maximum Cr(VI) biosorption capacities were found to be 17.3, 6.73, 14.0, 23.8, and 29.6?mg/g for the free algal cells, and alginate, alginate?Cgelatin, alginate?Ccells, and alginate?Cgelatin?Ccells at pH?2.0, which are corresponding to an initial Cr(VI) concentration of 400?mg/L. The biosorption of Cr(VI) on all the tested biosorbents (P. boryanum cells, alginate, alginate?Cgelatin, and alginate?Ccells, alginate?Cgelatin?Ccells) followed Langmuir adsorption isotherm model.

Conclusion

The thermodynamic studies indicated that the biosorption process was spontaneous and endothermic in nature under studied conditions. For all the tested biosorbents, biosorption kinetic was best described by the pseudo-second-order model.     

Occurrence of cyclophosphamide and epirubicin in wastewaters by direct injection analysis–liquid chromatography–high-resolution mass spectrometry

Background, aim, and scope

According to the high incidence of cancer worldwide, the amount of cytostatic drugs administered to patients has increased. These compounds are excreted to wastewaters, and therefore become potential water contaminants. At this stage, very little is known on the presence and elimination of cytostatic compounds in wastewater treatment plants (WWTP). The aim of this study was to develop a liquid chromatography?Chigh-resolution mass spectrometry (LC?COrbitrap?CMS) method for the determination of cyclophosphamide and epirubicin in wastewaters. These compounds represent two outmost used cytostatic agents.

Materials and methods

Extraction and analytical conditions were optimized for cyclophosphamide and epirubicin in wastewater. Both solid-phase extraction using Oasis 200?mg hydrophilic?Clipophilic balanced (HLB) cartridges and direct injection analysis were evaluated. Mass spectral characterization and fragmentation conditions were optimized at 50,000 resolving power (full width at half maximum, m/z 200) to obtain maximum sensitivity and identification performance. Quality parameters (recoveries, limits of detection, and repetitivity) of the methods developed were determined, and best performance was obtained with direct water analysis of the centrifuged wastewater. Finally, this method was applied to determine the presence of cyclophosphamide and epirubicin in wastewaters from a hospital effluent, an urban effluent, and influents and effluents from three WWTP.

Results and discussion

Cyclophosphamide and epirubicin were recovered after 50?mL preconcentration on solid-phase extraction 200?mg Oasis HLB cartridges (87% and 37%, respectively), and no breakthrough was observed by extracting 500?mL of water. Limits of detection were of 0.35 and 2.77?ng/L for cyclophosphamide and epirubicin, respectively. On the other hand, direct injection of water spiked at 1???g/L provided recoveries of 107% for cyclophosphamide and 44% for epirubicin and limits of detection from 3.1 to 85?ng?L^?1, respectively. The analysis of wastewaters using direct injection analysis revealed the presence of cyclophosphamide and epirubicin in WWTP influents and hospital and urban effluents at levels ranging from 5.73 to 24.8???g?L^?1.

Conclusions

The results obtained in this study demonstrate the capability of LC?COrbitrap?CMS for accurate trace analysis of these very polar contaminants. This method permitted to identify cyclophosphamide and epirubicin in wastewaters and influents of WWTP, but no traces were detected in WWTP effluents. The methodology herein developed is sensitive and robust and applicable for screening of a large number of samples since no preconcentration is needed.     

Isolation and characterization of 3-nitrophenol-degrading bacteria associated with rhizosphere of Spirodela polyrrhiza

Introduction

The accelerated biodegradation of 3-nitrophenol (3-NP) in the rhizosphere of giant duckweed (Spirodela polyrrhiza) was investigated.

Materials and methods

Biodegradation of 3-nitrophenol in the rhizosphere of a floating aquatic plant, S. polyrrhiza, was investigated by using three river water samples supplemented with 10?mg?l^?1 of 3-NP. Isolation and enrichment culture of 3-NP-degrading bacteria were performed in basal salts medium containing 3-NP (50?mg?l^?1). The isolated strains were physiologically and phylogenetically characterized by using an API20NE kit and 16S rRNA gene sequencing.

Results and discussion

Accelerated removal of 3-NP (100%) was observed in river water samples with S. polyrrhiza compared with their removal in plant-free river water. Also, 3-NP persisted in an autoclaved solution with aseptic plants, suggesting that the accelerated 3-NP removal resulted largely from degradation by bacteria inhabiting the plant rather than from adsorption and uptake by the plant. We successfully isolated six and four strains of 3-NP-degrading bacteria from the roots of S. polyrrhiza and plant-free river water, respectively. Phylogenetic analysis based on 16S rRNA gene divided the 3-NP-degrading bacteria into two taxonomic groups: the genera Pseudomonas and Cupriavidus. The strains belonging to the genus Cupriavidus were only isolated from the roots of duckweed. All strains isolated from the roots utilized 3-NP (0.5?mM) as a sole carbon and energy source, indicating that they could have contributed to the accelerated degradation of 3-NP in the rhizosphere of S. polyrrhiza.

Conclusions

The rhizoremediation using S. polyrrhiza and its rhizosphere bacteria can be an effective strategy for cleaning up the 3-NP-contaminated surface waters.