Heavy metal (Cd, Cr, Cu, Hg, Pb, Zn) concentrations in seven fish species in relation to fish size and location along the Yangtze River

Purpose

The objective of this paper is to assess the regulation of the accumulation of heavy metals in the aquatic environment and different fish species.

Methods

Water and fish samples were collected from upper to lower reaches of the Yangtze River. The heavy metal (Cd, Cr, Cu, Hg, Pb, Zn) concentrations in the muscle tissue of seven fishes were measured. Additionally, the relationships between heavy metal concentrations in fish tissue and fish size (length and weight), condition factor, water layer distribution, and trophic level were investigated.

Results

Metal concentrations (milligrams per kilogram wet weight) were found to be distributed differently among different fish species. The highest concentrations of Cu (1.22?mg/kg) and Zn (7.55?mg/kg) were measured in Pelteobagrus fulvidraco, the highest concentrations of Cd (0.115?mg/kg) and Hg (0.0304?mg/kg) were measured in Silurus asotus, and the highest concentrations of Pb (0.811?mg/kg) and Cr (0.239?mg/kg) were measured in Carassius auratus and Cyprinus carpio. A positive relationship was found between fish size and metal level in most cases. The variance of the relationships may be the result of differences in habitat, swimming behavior, and metabolic activity. In this study, fishes living in the lower water layer and river bottom had higher metals concentrations than in upper and middle layers. Benthic carnivorous and euryphagous fish had higher metals concentrations than phytoplankton and herbivorous fish. Generally, fish caught from the lower reach had higher metals concentrations than those from the upper reach.

Conclusions

Cadmium and lead concentrations in several fishes exceeded the permissible food consumption limits, this should be considered to be an important warning signal.     

Airborne lead levels in the Korean peninsula: characterization of temporal and spatial patterns and cancer risk analysis

Introduction

This study collected long-term airborne lead concentrations in the Korean peninsula and analyzed their temporal, spatial, and cancer risk characterization.

Methods

Approximately, 12,000 airborne samples of total suspended particulate (TSP) were collected from 30 ambient air monitoring stations in inland (Daegu, Daejeon, Gwangju, and Seoul) cities and portal cities (Incheon, Busan, and Ulsan) over a period of 7?years (2004?C2010). High volume air samplers were employed to collect daily TSP samples during the second week of the consecutive months throughout the entire study period. The concentrations of Pb extracted from the TSP samples were analyzed using either inductively coupled plasma-atomic emission or flame atomic absorption spectrometry.

Results

The long-term high mean Pb concentrations were observed in the port cities including Incheon (88?±?18?ng/m³), Ulsan (61?±?7?ng/m³), and Busan (58?±?6?ng/m³). In the temporal analysis, seasonal mean Pb levels were relatively higher in winter and spring than those in summer and fall. In the spatial analysis, the mean Pb levels in spring, winter, and fall from Incheon, which showed the highest seasonal concentrations except summer, were 110?±?19, 101?±?18, and 76?±?23?ng/m³, respectively. In summer, the highest seasonal mean Pb level was observed in the largest industrial city and the second port city, Ulsan (78?±?15?ng/m³), followed by Incheon (65?±?13?ng/m³).

Conclusion

The estimated excess cancer risk analysis showed that inhalation of Pb could result in cancer for one or two persons per million of population in the Korean peninsula.     

Enhancement of natural radioactivity in fertilized soil of Faisalabad, Pakistan

Background, goal, and scope

Natural radioactivity in phosphate rock (PR) is transferred to phosphate fertilizer (PF) during the manufacturing process of the PF. The continuous addition of the PF to the cultivated soil accumulates the radionuclides in the land and increases the level of radioactivity in the soil. The purpose of the present study was to investigate the enhanced level of accumulated radioactivity due to the continuous addition of the PF in the farmlands of Nuclear Institute of Agriculture and Biology (NIAB) at Faisalabad in Pakistan. The selected study area consisted of the highly fertilized farmlands and an unfertilized barren land of the NIAB.

Introduction

The understudy area is very fertile for the growth of various types of crops; therefore, four agricultural research institutes have been established at Faisalabad and NIAB is one of those. The NIAB has developed various research farmlands at different places in Pakistan. The crop yield has been increased by adding various fertilizers in the farmlands. The addition of the PF accompanied with the radionuclides enhances radioactivity in the fields. Human being is exposed directly or indirectly to this radiological hazard. A prolong exposure may become a cause of health risk.

Materials and methods

The area of study consisted of three types of lands: the land under cultivation for the last 40 and 30?years called Site 1 and Site 2, respectively, and the barren land was called Site 3. A total of 75 soil samples were collected within the crop rooting zone (up to 25?cm deep) of the soil of the NIAB farms. The samples were dried, pulverized to powder, sealed in plastic containers, and stored to achieve equilibrium between ²²⁶Ra and ²²²Rn. Activity concentrations of the radionuclides ²³⁸U (²²⁶Ra), ²³²Th, and ⁴⁰K in soil samples were determined by using a high resolution gamma ray spectrometry system, consisting of an high purity germanium detector coupled through a spectroscopy amplifier with a PC based MCA installed with Geni-2000 software.

Results

The measured activity concentration levels of ⁴⁰K were 662?±?15, 615?±?17, and 458?±?20?Bq?kg^?1, ²²⁶Ra were 48?±?6, 43?±?5, and 26?±?4?Bq?kg^?1, and that of ²³²Th were 39?±?5, 37?±?5, 35?±?5?Bq?kg^?1, respectively, in the soil of the Sites 1, 2, and 3. Gamma dose rate 1?m above the soil surface was 55, 51, and 40?nGy?h^?1 from Sites 1, 2, and 3, respectively. External dose rates in the rooms constructed of the bricks made of the soil from Sites 1, 2, and 3 were 161, 149, and 114?nGyh^?1, respectively.

Discussions

Activity concentration values of ⁴⁰K and ²²⁶Ra in the soil of Sites 1 and 2 were higher than that in the soil of Site 3. The relative rise of ⁴⁰K was 43?% and 34?% and that of ²²⁶Ra was 85?% and 65?% respectively in these sites. Activity concentrations of ²³²Th in all these sites were in the background range. Gamma dose rate 1?m above soil surface of Sites 1 and 2 was 40?% and 30?% respectively higher than that from the soil of Site 3. The rise in activity of ⁴⁰K and ²²⁶Ra and gamma dose from the Site 1 was greater than that from the Site 2. The least activity and dose were observed from the Site 3. Gamma dose in the dwellings made of fertilized soil bricks of Site 1 and Site 2 were respectively calculated to be 41?% and 32?% higher than that in the abodes made of unfertilized soil bricks of Site 3.

Conclusions

Activity concentrations of ²²⁶Ra and ⁴⁰K were observed to be enhanced in the fertilized farmlands of the NIAB. Outdoor and indoor gamma dose as radiological hazard were found to be increasing with the continuous addition of PF in the understudy farmlands.

Recommendations

It is recommended that naturally occurring radioactive metal should be removed during the process of manufacturing of the PF from the PR.

Prospective

The rise in radioactivity in the farmlands due to the addition of the PF can be a source of direct or indirect exposure to radiation that may enhance cancer risk of the exposed individuals.     

Identification of rice cultivar with exclusive characteristic to Cd using a field-polluted soil and its foreground application

Using low-accumulative plant, especially excluder crop, to safely produce food is one of the very important technologies of phytoremediation, which is practical to safe production and long-term remediation of heavy metal-contaminated soil. A pot experiment using field cadmium (Cd)-contaminated soil (Cd concentration was 0.75 mg?kg^?1) was conducted to compare Cd accumulation differences among 39 normal rice cultivars (Japonica) in Shenyang region of China for food safety and high grain yield aim. The results showed that brown grain Cd concentration in 12 rice cultivars of a total of 39 tested cultivars was lower than 0.2 mg?kg^?1 (Agricultural Trade Standard of Nonpollution Food for Rice of China, NY 5115–2008). In these 12 cultivars, Cd enrichment factors (Cd concentration ratio in shoot to that in soil) of nine cultivars were lower than 1. Likewise, Cd translocation factors (Cd concentration ratio in shoot to that in root) of eight cultivars were lower than the 0.28 average. Furthermore, grain yield per pot of seven cultivars were higher than the average 18.4 g?pot^?1. Four cultivars, i.e., Shendao 5, Tianfu 1, Fuhe 90, and Yanfeng 47 showed Cd-exclusive characteristic and better foreground application.     

Copper chitosan nanocomposite: synthesis, characterization, and application in removal of organophosphorous pesticide from agricultural runoff

Purpose

Removal of malathion from agricultural runoff was studied using novel copper-coated chitosan nanocomposite (CuCH)??a biopolymeric waste obtained from marine industry.

Methods

Synthesis and characterization of the adsorbent using different spectral techniques like Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy, energy-dispersive X-ray spectroscopy, Brunauer, Emmett, and Teller surface analyzer have been carried out. Equilibrium studies have been carried out to optimize the dose rate, pH, and the reaction time. Parathion and methyl parathion removal were also evaluated by CuCH in the batch mode. Using gas chromatography?Cmass spectrometry (GC?CMS) and FTIR studies suitable mechanism for adsorption has been suggested.

Results

The particle size of the adsorbent ranged from 700 to 750?nm. The surface area was found to be 20?m²?g^-1 with a pore volume of 0.11?cc?g^-1. The maximum adsorption capacity of malathion by CuCH was found to be 322.6?±?3.5?mg?g^-1 at an optimum pH of 2.0. Presence of copper ions enhanced the adsorption capacity of the adsorbent. The reaction was found to follow pseudo second-order kinetics with a rate constant of 0.53?g?mg^-1?min^-1. Evidence from FTIR indicated that copper ions form a dithionate complex with malathion during the adsorption stage. The adsorbent was found to remove malathion completely from spiked concentration of 2?mg?l^-1 in the agricultural run-off samples. It was also found that CuCH removed other organophospurous pesticides like methyl parathion and parathion under prevailing conditions.

Conclusions

The results indicated that CuCH could be applied for the removal of organophosphorous pesticides.     

Equilibrium, kinetic, and thermodynamic biosorption of Pb(II), Cr(III), and Cd(II) ions by dead anaerobic biomass from synthetic wastewater

Purpose

Heavy metals are toxic pollutants released into the environment as a result of different industrial activities. Biosorption of heavy metals from aqueous solutions is a new technology for the treatment of industrial wastewater. The aim of the present research is to highlight the basic biosorption theory to heavy metal removal.

Materials and methods

Heterogeneous cultures mostly dried anaerobic bacteria, yeast (fungi), and protozoa were used as low-cost material to remove metallic cations Pb(II), Cr(III), and Cd(II) from synthetic wastewater. Competitive biosorption of these metals was studied.

Results

The main biosorption mechanisms were complexation and physical adsorption onto natural active functional groups. It is observed that biosorption of these metals was a surface process. The main functional groups involved in these processes were hydroxyl (–OH) and carboxylic groups (C=O) with 37, 52, and 31 and 21, 14, and 34 % removal of Pb(II), Cr(III), and Cd(II), respectively. Langmuir was the best model for a single system. While extended Langmuir was the best model for binary and ternary metal systems. The maximum uptake capacities were 54.92, 34.78, and 29.99 mg/g and pore diffusion coefficients were 7.23, 3.15, and 2.76?×?10^?11 m²/s for Pb(II), Cr(III), and Cd(II), respectively. Optimum pH was found to be 4. Pseudo-second-order was the best model to predict the kinetic process. Biosorption process was exothermic and physical in nature.

Conclusions

Pb(II) offers the strongest component that is able to displace Cr(III) and Cd(II) from their sites, while Cd(II) ions are the weakest adsorbed component.     

Optimization of nitrate reduction by EDTA catalyzed zero-valent bimetallic nanoparticles in aqueous medium

The present study aims to investigate the EDTA catalyzed reduction of nitrate (NO ₃ ^? ) by zero-valent bimetallic (Fe?CAg) nanoparticles (ZVBMNPs) in aqueous medium and to enumerate the effect of temperature, solution pH, ZVBMNPs dose and EDTA concentration on NO ₃ ^? reduction. Batch experimental data were generated using a four-factor Box?CBehnken design. Optimization modeling was performed using the response surface method for maximizing the reduction of NO ₃ ^? by ZVBMNPs. Significance of the independent variables and their interactions were tested by the analysis of variance and t test statistics. The model predicted maximum reduction capacity (340.15?mg?g^?1 NO ₃ ^? ) under the optimum conditions of temperature, 60?°C; pH?4; dose, 1.0?g?l^?1; and EDTA concentration, 2.0?mmol?l^?1 was very close to the experimental value (338.62?mg?g^?1) and about 16?% higher than the experimentally determined capacity (291.32?mg?g^?1). Study demonstrated that ZVBMNPs had higher reduction efficiency than Fe⁰ nanoparticles for NO ₃ ^? . EDTA significantly enhanced the NO ₃ ^? reduction by ZVBMNPs. The EDTA catalyzed reduction of NO ₃ ^? by ZVBMNPs can be employed for the effective decontamination of water.     

Diphenyl diselenide attenuates hepatic and hematologic toxicity induced by chlorpyrifos acute exposure in rats

Purpose

In this study, we investigated the effect of diphenyl diselenide [(PhSe)₂] on chlorpyrifos (CPF)-induced hepatic and hematologic toxicity in rats.

Methods

Rats were pre-treated with (PhSe)₂ (5?mg/kg) via the oral route (oral gavage) once a day for 7?days. On the eighth and ninth days, rats were treated with (PhSe)₂ (5?mg/kg) 30?min prior to CPF (50?mg/kg, by subcutaneous route). The aspartate aminotransferase, alanine aminotransferase, and lactate dehydrogenase activities were determined in plasma of rats. Lipid peroxidation, protein carbonyl, and non-protein thiol levels as well as catalase, superoxide dismutase, glutathione peroxidase, glutathione reductase, and gluthatione S-transferase activities were determined in livers of rats. Hematological parameters were also determined.

Results

The results showed that CPF caused hepatic oxidative damage, as demonstrated by an increase in lipid peroxidation and protein carbonyl levels which was associated with a decrease in antioxidant defenses. CPF exposure caused a reduction in the leukocyte, indicating hematologic toxicity. (PhSe)₂ was effective in attenuating these toxic effects caused by CPF exposure in rats.

Conclusions

The results indicated that (PhSe)₂ was effective in protecting the hepatic and hematologic toxicity induced by acute CPF exposure in rats.     

Aquatic photochemistry of paracetamol in the presence of dissolved organic chromophoric material and nitrate

Purpose

This study contains some new findings connected to the photolysis of the drug paracetamol (hereinafter APAP) especially in light of estimating natural conditions, and it will offer information to better evaluate environmental problems connected with this widely used analgesic agent. Only a few studies, so far, have focussed on the photodegradation process of APAP in the natural environment, and the question about the role of the colored/chromophoric dissolved organic matter (CDOM) and nitrate (NO ₃ ^? ) as photoinductors is almost open.

Methods

APAP dissolved in freshwater and pure laboratory water in the presence and absence of CDOM and NO ₃ ^? ions was irradiated using weak-energy photon energies simulating natural conditions.

Results

CDOM and NO ₃ ^? as photoinductors produced only the slow phototransformation of APAP under weak energy radiation, and APAP seemed to be practically resistant to direct photolysis under weak radiant energies available in natural conditions. The estimated reaction efficiencies, in addition to half-lives, speak for that NO ₃ ^? and CDOM do not act as quite independent photoinductors but their effect in conjunction (CDOM?CNO ₃ ^? ?Cwater) is stronger than the separate ones. The principal phototransformation intermediates of APAP were mono-hydroxy derivatives, depending on available photon energies formed via ortho- or meta-hydroxylation, possessing substantial power of resistance to further specific transformation reactions.

Conclusions

The estimated half-life of the phototransformation of APAP in the natural aqueous environment and in the presence of suitable photoinductors will be about 30?days or more.     

Removal of Cu, Zn, and Cd from aqueous solutions by the dairy manure-derived biochar

Purpose

Biochar derived from waste biomass is now gaining much attention for its function as a biosorbent for environmental remediation. The objective of this study was to determine the effectiveness of biochar as a sorbent in removing Cd, Cu, and Zn from aqueous solutions.

Methods

Biochar was produced from dairy manure (DM) at two temperatures: 200°C and 350°C, referred to as DM200 and DM350, respectively. The obtained biochars were then equilibrated with 0–5 mM Cu, Zn or Cd in 0.01 M NaNO₃ solution for 10 h. The changes in solution metal concentrations after sorption were evaluated for sorption capacity using isotherm modeling and chemical speciation Visual MINTEQ modeling, while the solid was collected for species characterization using infrared spectroscopy and X-ray elemental dot mapping techniques.

Results

The isotherms of Cu, Zn, and Cd sorption by DM200 were better fitted to Langmuir model, whereas Freundlich model well described the sorption of the three metals by DM350. The DM350 were more effective in sorbing all three metals than DM200 with both biochars had the highest affinity for Cu, followed by Zn and Cd. The maximum sorption capacities of Cu, Zn, and Cd by DM200 were 48.4, 31.6, and 31.9 mg g^?1, respectively, and those of Cu, Zn, and Cd by DM350 were 54.4, 32.8, and 51.4 mg g^?1, respectively. Sorption of the metals by the biochar was mainly attributed to their precipitation with PO ₄ ^3? or CO ₃ ^2? originating in biochar, with less to the surface complexation through –OH groups or delocalized π electrons. At the initial metal concentration of 5 mM, 80–100 % of Cu, Zn, and Cd retention by DM200 resulted from the precipitation, with less than 20 % from surface adsorption through phenonic –OH complexation. Among the precipitation, 20–30 % of the precipitation occurred as metal phosphate and 70–80 % as metal carbonate. For DM350, 75–100 % of Cu, Zn, and Cd retention were due to the precipitation, with less than 25 % to surface adsorption through complexation of heavy metal by phenonic –OH site or delocalized π electrons. Among the precipitation, only less than 10 % of the precipitation was present as metal phosphate and more than 90 % as metal carbonate.

Conclusions

Results indicated that dairy manure waste can be converted into value-added biochar as a sorbent for sorption of heavy metals, and the mineral components originated in the biochar play an important role in the biochar's high sorption capacity.     

Reduction of dinitrotoluene sulfonates in TNT red water using nanoscale zerovalent iron particles

Purpose

This research was designed to investigate the feasibility of converting the dinitrotoluene sulfonates (DNTS) in TNT red water into the corresponding aromatic amino compounds using nanoscale zerovalent iron (NZVI).

Methods

NZVI particles were simultaneously synthesized and stabilized by sodium borohydride reduction in a nondeoxygenated system. The morphology, elemental content, specific surface area, and crystal properties of the NZVI were characterized before and after the reaction by environmental scanning electron microscope; energy dispersive X-ray; Brunauer, Emmett, and Teller; and X-ray diffraction, respectively. The reduction process was conducted at pH?=?6.3 at ambient temperature. The efficiency of the NZVI-mediated DNTS reduction process was monitored by HPLC, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy analyses.

Results

The properties of the NZVI particles prepared were found to be similar to those obtained through oxygen-free preparation and inert stabilization processes. Both 2,4-DNT-3-sulfonate (2,220?mg?L^?1) and 2,4-DNT-5-sulfonate (3,270?mg?L^?1) in TNT red water underwent a pseudo-first-order transformation when mixed with NZVI at room temperature and near-neutral pH. Their observed rate constants were 0.11 and 0.30?min^?1, respectively. Within 1?h of processing, more than 99% of DNTS was converted by NZVI-mediated reduction into the corresponding diaminotoluene sulfonates.

Conclusions

NZVI can be simultaneously prepared and stabilized in a nondeoxygenated system. NZVI reduction is a highly efficient method for the conversion of DNTS into the corresponding diaminotoluene sulfonates under near-neutral pH conditions. Therefore, NZVI reduction may be useful in the treatment of TNT red water and subsequent recovery of diaminotoluene from explosive wastewater.     

Remediation of 4-nonylphenol in aqueous solution by using free radicals generated by the oxidative reactions

Introduction

This study relates to use of zerovalent iron to generate hydroxyl free radicals and undergo subsequent oxidation to destroy 4-nonylphenol (NP) by mild process in aqueous solution and activation of oxygen gas (O₂) at room temperature. This technology is based on a novel oxidative mechanism mediated by zerovalent iron rather than commonly used reduction mechanism.

Materials and methods

A laboratory scale device consisting of a 250?ml pyrex serum vials fixed to a Vortex agitator was used. Different amounts of zerovalent iron powder (ZVI; 1, 10, and 30?g/l) at pH?4 and room temperature with bubbling of oxygen gas were investigated.

Results and conclusion

Experiments showed an observed degradation rate k _(obs) directly proportional to the amount of iron. 4-Nonylphenol degradation reactions demonstrated first-order kinetics with a half-life of about 10.5?±?0.5 and 3.5?±?0.2?min when experiments were conducted at [ZVI]?=?1 and 30?g/l respectively. Three analytical techniques were employed to monitor 4-nonylphenol degradation and mineralization: (1) spectrofluorimetry; (2) high-performance liquid chromatography; (3) total organic carbon meter (TOC meter). Results showed a complete disappearance of 4-nonylphenol after 20?min of contact with ZVI. The intermediate by-products of the reaction were not identified but the disappearance of NP was monitored by the three above-mentioned techniques.     

Modeling and optimization of reductive degradation of chloramphenicol in aqueous solution by zero-valent bimetallic nanoparticles

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?Csilver 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.     

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.     

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.     

Acute effect of benzo[a]anthracene on the biodegradation of peptone under aerobic conditions

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.     

Influence of sediment acidification on the bioaccumulation of metals in Ruditapes philippinarum

Background, aim and scope

The influence of pH (range 6.5–8.5) on the uptake of Zn, Cd, Pb, Cu, Ni, Cr, Hg, and As by juveniles of the clam Ruditapes philippinarum was examined in order to understand whether variation in sediment pH has significant repercussions on metal bioaccumulation.

Materials and methods

Clams were exposed to sediments collected in three locations in the Gulf of Cadiz (Huelva, Guadalquivir and Bay of Cadiz) and to contaminated particles derived from an accidental mining spill in Spain.

Results

With a notable exception of metal Cd, the concentration of metals within clams significantly increased (p?<?0.1) when sediment pH was lowered by one or two units. Moreover, the magnitude of this effect was dependent on the type of sediment contamination.

Discussion

Lower pH increases metal solubility and reduces or invert the metal sorption of metals to sediments. Increases in free metal ions in water favors metal uptake by clams, hence pH is an important factor controlling the mobility of these metals within sediments and their subsequent bioaccumulation within biota. Although sediment-water exchange of Cd can increase with acidification, this excess may be counterbalanced by the presence of ligands in seawater preventing the uptake by organism. Besides chlorines, Cd has also an affinity with carbonates and other ligands present in sea water. These Cd-carbonate complexes may reduce the bioavailable to organisms.

Conclusions

These results highlight the potential implications of sediment acidification, either due to the storage excess of organic matter or to the forced capture of CO₂, on the increasing metal availability to benthic organisms.

Recommendations and perspectives

This kind of studies should be increased to address the influence of acidification in the behavior, bioavailability, toxicity, and risk assessment of contaminants associated with sediments either above sub-seabed geological formations in marine environments or in high enriched by organic matter in estuarine areas. Recently, the capture of CO₂ in marine environments has been approved and started; it is necessary to address the potential impacts associated with leakages or other events occurring during the procedure of injection and storage of CO2.     

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.     

Degradation and mineralization of sulcotrione and mesotrione in aqueous medium by the electro-Fenton process: a kinetic study

Introduction

The degradation and mineralization of two triketone (TRK) herbicides, including sulcotrione and mesotrione, by the electro-Fenton process (electro-Fenton using Pt anode (EF-Pt), electro-Fenton with BDD anode (EF-BDD) and anodic oxidation with BDD anode) were investigated in acidic aqueous medium.

Methods

The reactivity of both herbicides toward hydroxyl radicals was found to depend on the electron-withdrawing effect of the aromatic chlorine or nitro substituents. The degradation of sulcotrione and mesotrione obeyed apparent first-order reaction kinetics, and their absolute rate constants with hydroxyl radicals at pH?3.0 were determined by the competitive kinetics method.

Results and discussion

The hydroxylation absolute rate constant (k _abs) values of both TRK herbicides ranged from 8.20?×?10⁸ (sulcotrione) to 1.01?×?10⁹ (mesotrione) L?mol^?1?s^?1, whereas those of the TRK main cyclic or aromatic by-products, namely cyclohexane 1,3-dione , (2-chloro-4-methylsulphonyl) benzoic acid and 4-(methylsulphonyl)-2-nitrobenzoic acid, comprised between 5.90?×?10⁸ and 3.29?×?10⁹?L?mol^?1?s^?1. The efficiency of mineralization of aqueous solutions of both TRK herbicides was evaluated in terms of total organic carbon removal. Mineralization yields of about 97?C98% were reached in optimal conditions for a 6-h electro-Fenton treatment time.

Conclusions

The mineralization process steps involved the oxidative opening of the aromatic or cyclic TRK by-products, leading to the formation of short-chain carboxylic acids, and, then, of carbon dioxide and inorganic ions.     

Lead concentration increase in the hepatic and gill soluble fractions of European chub (Squalius cephalus)—an indicator of increased Pb exposure from the river water

Purpose

To examine if chronic exposure of feral fish to elevated Pb concentrations in the river water (up to 1???g?L^?1), which are still lower than European recommendations for dissolved Pb in surface waters (7.2???g?L^?1; EPCEU (Official J L 348:84, 2008)), would result in Pb accumulation in selected fish tissues.

Methods

Lead concentrations were determined by use of HR ICP-MS in the gill and hepatic soluble fractions of European chub (Squalius cephalus) caught in the Sutla River (Croatia?CSlovenia).

Results

At the site with increased dissolved Pb in the river water, soluble gill Pb levels (17.3???g?L^?1) were approximately 20 times higher compared to uncontaminated sites (0.85???g?L^?1), whereas the ratio between contaminated (18.1???g?L^?1) and uncontaminated sites (1.17???g?L^?1) was lower for liver (15.5). Physiological variability of basal Pb concentrations in soluble gill and hepatic fractions associated to fish size, condition, sex, or age was not observed, excluding the possibility that Pb increase in chub tissues at contaminated site could be the consequence of studied biotic parameters. However, in both tissues of Pb-exposed specimens, females accumulated somewhat more Pb than males, making female chubs potentially more susceptible to possible toxic effects.

Conclusions

The fact that Pb increase in gill and hepatic soluble fractions of the European chub was not caused by biotic factors and was spatially restricted to one site with increased dissolved Pb concentration in the river water points to the applicability of this parameter as early indicator of Pb exposure in monitoring of natural waters.