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.     

Characteristics of precipitation chemistry at Lushan Mountain, East China: 1992–2009

Introduction

Trends in precipitation pH and conductivity during 1992?C2009, and in ionic compositions from January 2007 to June 2009, are reported from Lushan Mountain, one of the highest mountains in mid-east China. Annual mean pH was in the range of 4.35?C5.01 and showed a statistically very significant (P?P?Results and discussions Over the period of study, Lushan Mountain received more rainfall in spring and summer. The pH values varied seasonally with winter minima. The winter multiyear seasonal mean pH was 4.35. The corresponding summer value was 4.88. SO ₄ ^2? and NO ₃ ^? were the main anions, and NH ₄ ⁺ and Ca²⁺ the main cations. The anion to cation ratio was 0.8?C1.0, and that of [SO ₄ ^2? ] to [NO ₃ ^? ] was 2.4-3.0, much lower than that of the 1980s. However, sulfuric acid was still the main acid present. The ratio of [NH ₄ ⁺ ] to [Ca²⁺] was about 1.0, suggesting that these two alkaline substances provided close acid neutralizing capacity. The ratio of [Cl^?] to [Na⁺] was about 0.67, somewhat lower than that of natural precipitation.

Conclusions

Ionic composition varied seasonally and was closely correlated to the amounts of rainfall and pollution. Trajectory analyses showed that the trajectories to Lushan Mountain could be classified in six clusters and trajectories originating from the South Sea and the areas surrounding Lushan Mountain had the greatest impacts on precipitation chemistry.     

Characterization of PM10 atmospheric aerosol at urban and urban background sites in Fuzhou city, China

Background

PM₁₀ aerosol samples were simultaneously collected at two urban and one urban background sites in Fuzhou city during two sampling campaigns in summer and winter. PM₁₀ mass concentrations and chemical compositions were determined.

Methods

Water-soluble inorganic ions (Cl^?, NO ₃ ^? , SO ₄ ^2? , NH ₄ ⁺ , K⁺, Na⁺, Ca²⁺, and Mg²⁺), carbonaceous species (elemental carbon and organic carbon), and elements (Al, Si, Mg, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Br, and Pb) were detected using ion chromatography, thermal/optical reflectance, and proton-induced X-ray emission methods, respectively.

Results

PM₁₀ mass concentrations, as well as most of the chemical components, were significantly increased from urban background to urban sites, which were due to enhanced anthropogenic activities in urban areas. Elements, carbonaceous species, and most of the ions were more uniformly distributed at different types of sites in winter, whereas secondary ion SO ₄ ^2? , NO ₃ ^? , and NH ₄ ⁺ showed more evident urban-background contrast in this season. The chemical mass closure indicated that mineral dust, organic matters, and sulfate were the most abundant components in PM₁₀. The sum of individually measured components accounted for 86.9?C97.7% of the total measured PM₁₀ concentration, and the discrepancy was larger in urban area than in urban background area.

Conclusion

According to the principal component analysis?Cmultivariate linear regression model, mineral dust, secondary inorganic ions, sea salt, and motor vehicle were mainly responsible for the PM₁₀ particles in Fuzhou atmosphere, and contributed 19.9%, 53.3%, 21.3%, and 5.5% of PM₁₀, respectively.     

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.     

Microbial structure and chemical components of aerosols caused by rotating brushes in a wastewater treatment plant

Purpose

Bacterial community structure and the chemical components in aerosols caused by rotating brushes in an Orbal oxidation ditch were assessed in a Beijing municipal wastewater treatment plant.

Methods

Air samples were collected at different distances from the aerosol-generating rotating brushes. Molecular culture-independent methods were used to characterize the community structure of the airborne bacteria in each sample regardless of cell culturability. A clone library of 16S rDNA directly amplified from air DNA of each sample was constructed and sequenced to analyze the community composition and diversity. Insoluble particles and water-soluble ions emitted with microorganisms in aerosols were analysis by a scanning electron microscope together with energy dispersive X-ray spectroscopy and ion chromatogram analyzer.

Results

In total, most of the identified bacteria were Proteobacteria. The majority of sequences near the rotating brushes (the main source of the bioaerosols) were Proteobacteria (62.97 %) with ??-(18.52 %) and ??-(44.45?%) subgroups and Bacteroidetes (29.63 %). Complex patterns were observed for each sampling location, suggesting a highly diverse community structure, comparable to that found in water in the Orbal oxidation ditch. Accompany with microorganisms, 46.36???g/m³ of SO ₄ ^2? , 29.35???g/m³ of Cl^?, 21.51???g/m³ of NO ₃ ^? , 19.76???g/m³ of NH ₄ ⁺ , 11.42???g/m³ of PO ₄ ^3? , 6.18???g/m³ of NO ₂ ^? , and elements of Mg, Cl, K, Na, Fe, S, and P were detected from the air near the aerosols source.

Conclusions

Differences in the structure of the bacterial communities and chemical components in the aerosols observed between sampling sites indicated important site-related variability. The composition of microorganisms in water was one of the most important sources of bacterial communities in bioaerosols. Chemical components in bioaerosols may provide a media for airborne microorganism attachment, as well as a suitable microenvironment for their growth and survival in the air. This study will be benefit for the formulation of pollution standards, especially for aerosols, that take into account plant workers?? health.     

Identification of cadmium-excluding welsh onion (Allium fistulosum L.) cultivars and their mechanisms of low cadmium accumulation

Purpose

Screening out cadmium (Cd) excluding cultivars of a crop in agricultural production is an effective way to prohibit Cd entering into food chain.

Methods

A judging criterion for Cd-excluding cultivars based on food safety was suggested and used in the identification of Cd-excluding welsh onion (Allium fistulosum L.) cultivars. A pot culture experiment was carried out to screen out Cd-excluding cultivars, of which the results were confirmed by plot experiments. The relevant factors of Cd accumulation in the pseudostem were analyzed and used in the correlation analysis aiming to study the low Cd accumulation mechanisms.

Results

The concentration of Cd in the pseudostem of welsh onions was 0.08?C0.20, 0.18?C0.41, and 0.26?C0.61?mg/kg fresh weight (FW) under three treatments (1.0, 2.5, and 5.0?mg/kg), respectively. The significant (p? ₃ ^? ?CN, and eight other elements in the tested welsh onion cultivars. Two cultivars were identified as Cd-excluding cultivars, mainly because the accumulation of Cd in their pseudostem was only 0.041?±?0.003 and 0.046?±?0.002?mg/kg FW, and 0.054?±?0.001 and 0.066?±?0.011?mg/kg FW, when growing in plots with Cd concentration of 0.49 and 0.99?mg/kg, respectively.

Conclusions

Ribentiegancongwang and Wuyeqi could be identified as Cd-excluding cultivars. Low bioaccumulation factor of the roots was the main mechanism of Cd-excluding welsh onion cultivars.     

Novel insights in Al-MCM-41 precursor as adsorbent for regulated haloacetic acids and nitrate from water

High concentration of NO ₃ ^? in groundwater has raised concern over possible contamination of drinking water supplies. In addition, the formation of haloacetic acids (HAAs) as by-products during disinfection with chlorine-based agents is still a relevant issue, since HAAs pose serious health hazard. In this work, we investigated the affinity of a precursor of Al-MCM-41 (a mesostructured hexagonal aluminosilicate containing the template surfactant) towards nitrate and HAAs, for its possible application in the removal of these pollutants from natural and drinking waters. Additionally, adsorption kinetics and isotherms were studied. The adsorbent was synthesized using cetyltrimethylammonium bromide as surfactant and characterized by physico?Cchemical techniques. Simulated drinking water was spiked with the EPA-regulated HAAs (monochloroacetic (MCAA), monobromoacetic (MBAA), dichloroacetic (DCAA), dibromoacetic (DBAA), and trichloroacetic (TCAA) acids) and placed in contact with the adsorbent. The effect of matrix composition was studied. Adsorption kinetic studies were performed testing three kinetics models. For the adsorption studies, three adsorption isotherm approaches have been tested to experimental data. The pollutant recoveries were evaluated by suppressed ion chromatography. The affinity of the adsorbent was TCAA = DBAA = DCAA > MBAA > MCAA with DCAA, DBAA, and TCAA completely removed. A removal as high as 77?% was achieved for 13?mg/L nitrate. The adsorption isotherms of NO ₃ ^? and monochloroacetic acid can be modeled by the Freundlich equation, while their adsorption kinetics follow a pseudo-second-order rate mechanism. The adsorbent exhibited high affinity towards HAAs in simulated drinking water even at relevant matrix concentrations, suggesting its potential application for water remediation technologies.     

Influence of algal bloom degradation on nutrient release at the sediment–water interface in Lake Taihu, China

Algal bloom could drastically influence the nutrient cycling in lakes. To understand how the internal nutrient release responds to algal bloom decay, water and sediment columns were sampled at 22 sites from four distinct regions of China’s eutrophic Lake Taihu and incubated in the laboratory to examine the influence of massive algal bloom decay on nutrient release from sediment. The column experiment involved three treatments: (1) water and sediment (WS); (2) water and algal bloom (WA); and (3) water, sediment, and algal bloom (WSA). Concentrations of dissolved oxygen (DO), total nitrogen (TN), total phosphorus (TP), ammonium (NH ₄ ⁺ -N), and orthophosphate (PO ₄ ^3? -P) were recorded during incubation. The decay of algal material caused a more rapid decrease in DO than in the algae-free controls and led to significant increases in NH ₄ ⁺ -N and PO ₄ ^3? -P in the water. The presence of algae during the incubation had a regionally variable effect on sediment nutrient profiles. In the absence of decaying algae (treatment WS), sediment nutrient concentrations decreased during the incubation. In the presence of blooms (WSA), sediments from the river mouth released P to the overlying water, while sediments from other regions absorbed surplus P from the water. This experiment showed that large-scale algal decay will dramatically affect nutrient cycling at the sediment–water interface and would potentially transfer the function of sediment as “container” or “supplier” in Taihu, although oxygen exchange with atmosphere in lake water was stronger than in columns. The magnitude of the effect depends on the physical–chemical character of the sediments.     

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.     

Detection of DNA damage in fish Oreochromis mossambicus induced by co-exposure to phenanthrene and nitrite by ESI-MS/MS

Background, aim, and scope

Mutagenic nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) have been known to arise in the environment through direct emissions from combustion sources and nitration of PAHs, primarily in the atmosphere. In the marine environment, PAHs are one of the classic anthropogenic organic pollutants, while nitrite (NO ₂ ^– ) is produced naturally via various biological processes like imbalance in nitrification/denitrification or eutrophication and subsequent oxygen depletion from an oversupply of nutrients. In this paper, we report the formation of PAH-DNA adducts in fish contaminated with PAHs and exposed to NO ₂ ^– in the ambient water. Electrospray ionization tandem mass spectrometric (ESI-MS/MS) analysis of the bile of the euryhaline fish Oreochromis mossambicus exposed simultaneously to field relevant sublethal concentrations of phenanthrene and NO ₂ ^– and collision-induced dissociation of selected ions revealed the presence of DNA-PAH adducts. The present study indicates that, although several high sensitivity techniques have been developed for the analysis of PAH derived DNA adducts, MS/MS has emerged as a powerful tool in the detection and structure elucidation of DNA adducts.

Materials and methods

Juvenile O. mossambicus from a local estuarine fish farm were used with increasing frequency for carcinogenicity testing and comparative cancer research. The fish were exposed to the alkylating agent phenanthrene in the presence of NO ₂ ^– . Composite untreated bile samples after dilution with methanol: water (1:1; v/v) were analyzed by ESI-MS.

Results

Several adducts could be evidenced in the bile by MS/MS. Deoxyadenosine/deoxyguanosine having a mass in the range of 450–650 amu is detected. In addition, a segment of modified dinucleotide with a mass that corresponds to a dimer consisting of a modified guanosine and a normal guanosine has also been identified in the bile.

Discussion

The formation of certain types of DNA adducts is a crucial step in the induction of cancer and a primary stage in mutagenesis. Phenanthrene injected by i.p. route led to the transformation of phenanthrene to N-formyl amino phenanthrene-N ⁶-deoxyadenosine adduct, whereas the fish co-exposed to phenanthrene and ambient nitrite metabolizes PAH to mono-, di- as well as trinitro derivatives, which then react with DNA leading to the formation of mainly modified guanosine and adenosine adducts. In the present investigation, dinitrophenanthrene diol epoxide (DNPDE) adduct with guanosine (m/z 587) seems to be the dominant adduct in the mixture, and its presence is shown first as a comparatively less stable adduct, which decomposes to give a more stable N² adduct (m/z 567).

Conclusions

MS/MS has proved to be useful in the rapid determination and discrimination of structurally different phenanthrene/derivatives DNA adducts in a complex mixture of fish bile co-exposed to phenanthrene and nitrite. However, the nature of metabolites formed is likely determined by the route of PAH administration, and there is a need to further define the early biochemical events of carcinogenesis in these species.

Recommendations and perspectives

DNA adduct analysis in fish bile offers a promising approach to study the risk of potentiation of anthropogenic chemicals into genotoxic compounds in the presence of nitrite in the marine environment. We believe this is the first report on the formation of DNA-phenanthrene adducts on co-exposure of the fish to PAH and nitrite.     

Evaluation of environmental impact produced by different economic activities with the global pollution index

Introduction

The paper analyses the environment pollution state in different case studies of economic activities (i.e. co-generation electric and thermal power production, iron profile manufacturing, cement processing, waste landfilling, and wood furniture manufacturing), evaluating mainly the environmental cumulative impacts (e.g. cumulative impact against the health of the environment and different life forms).

Materials and methods

The status of the environment (air, water resources, soil, and noise) is analysed with respect to discharges such as gaseous discharges in the air, final effluents discharged in natural receiving basins or sewerage system, and discharges onto the soil together with the principal pollutants expressed by different environmental indicators corresponding to each specific productive activity. The alternative methodology of global pollution index (I _GP ^* ) for quantification of environmental impacts is applied.

Results and discussion

Environmental data analysis permits the identification of potential impact, prediction of significant impact, and evaluation of cumulative impact on a commensurate scale by evaluation scores (ES_i) for discharge quality, and global effect to the environment pollution state by calculation of the global pollution index (I _GP ^* ).

Conclusions

The I _GP ^* values for each productive unit (i.e. 1.664?C2.414) correspond to an ??environment modified by industrial/economic activity within admissible limits, having potential of generating discomfort effects??. The evaluation results are significant in view of future development of each productive unit and sustain the economic production in terms of environment protection with respect to a preventive environment protection scheme and continuous measures of pollution control.     

The influence of hydroxyl volatile organic compounds on the oxidation of aqueous sulfur dioxide by oxygen

Although the effect of volatile organic compounds (VOCs) on the oxidation of dissolved sulfur dioxide by oxygen has been the subject of many investigations, this is the first study which examines the effect of a large number of precisely 16 hydroxy compounds. The kinetics both in the absence and the presence of VOCs was defined by rate laws (A and B): A $$ \hbox{-} \mathrm{d}\left[\mathrm{S}\left(\mathrm{IV}\right)\right]/\mathrm{dt}={R}_o={k}_o\left[\mathrm{S}\left(\mathrm{IV}\right)\right] $$ B $$ \hbox{-} \mathrm{d}\left[\mathrm{S}\left(\mathrm{IV}\right)\right]/\mathrm{dt}={R}_i={k}_i\left[\mathrm{S}\left(\mathrm{IV}\right)\right] $$ where R _o and k _o are the initial rate and first-order rate constant, respectively, in the absence of VOCs, R _i , and k _i are the initial rate and the first-order rate constant, respectively, in the presence of VOCs, and [S(IV)] is the concentration of dissolved sulfur dioxide, sulfur(IV). The nature of the dependence of k _i on the concentration of inhibitor, [Inh], was defined by Eq. (C). C $$ {k}_i={k}_0/\left(1+B\left[\mathrm{Inh}\right]\right) $$ where B is an empirical inhibition parameter. The values of B have been determined from the plots of 1/k _i versus [Inh]. Among aliphatic and aromatic hydroxy compounds studied, t-butyl alcohol and pinacol were without any inhibition effect due to the absence of secondary or tertiary hydrogen. The values of inhibition parameter, B, were related to k _inh , the rate constant for the reaction of SO₄ ^? radical with the inhibitor, by Eq. (D). D $$ B=\left(9\pm 2\right)\times 1{0}^{-4}\times {k}_{inh} $$ Equation (D) may be used to calculate the values of either of B or k _inh provided that the other is known. The extent of inhibition depends on the value of the composite term, B[Inh]. However, in accordance with Eq. (C), the extent of inhibition would be sizeable and measurable when B[Inh]?>?0.1 and oxidation of S(IV) would be almost completely stopped when B[Inh]?≥?10. B[Inh] value can be used as a guide whether the reaction step: SO₄ ^??+?organics? \( \overset{k_{inh}}{\to } \) ?SO₄ ^2??+?non-chain products: should be included in the multiphase models or not.     

Removal mechanisms and kinetics of trace tetracycline by two types of activated sludge treating freshwater sewage and saline sewage

Understanding the removal mechanisms and kinetics of trace tetracycline by activated sludge is critical to both evaluation of tetracycline elimination in sewage treatment plants and risk assessment/management of tetracycline released to soil environment due to the application of biosolids as fertilizer. Adsorption is found to be the primary removal mechanism while biodegradation, volatilization, and hydrolysis can be ignored in this study. Adsorption kinetics was well described by pseudo-second-order model. Faster adsorption rate (k ₂?=?2.04?×?10^?2?g?min^?1?μg^?1) and greater adsorption capacity (q _e?=?38.8 μg?g^?1) were found in activated sludge treating freshwater sewage. Different adsorption rate and adsorption capacity resulted from chemical properties of sewage matrix rather than activated sludge surface characteristics. The decrease of tetracycline adsorption in saline sewage was mainly due to Mg²⁺ which significantly reduced adsorption distribution coefficient (K _d) from 12,990?±?260 to 4,690?±?180 L?kg^?1. Species-specific adsorption distribution coefficients followed the order of $ K_{\mathrm{d}}^{{ + 00}} \gg K_{\mathrm{d}}^{{ + - 0}} > K_{\mathrm{d}}^{{ + - - }} $ . Contribution of zwitterionic tetracycline to the overall adsorption was >90 % in the actual pH range in aeration tank. Adsorption of tetracycline in a wide range of temperature (10 to 35 °C) followed the Freundlich adsorption isotherm well.     

Removal of Cr(VI) onto Ficus carica biosorbent from water

The utilization of sustainable and biodegradable lignocellulosic fiber to detoxify the noxious Cr(VI) from wastewater is considered a versatile approach to clean up a contaminated aquatic environment. The aim of the present research is to assess the proficiency and mechanism of biosorption on Ficus carica bast fiber via isotherm models (Langmuir, Freundlich, Temkin, Harkin’s–Jura, and Dubinin–Radushkevich), kinetic models, and thermodynamic parameters. The biomass extracted from fig plant was characterized by scanning electron microscopy and Fourier-transform infrared spectroscopy. To optimize the maximum removal efficiency, different parameters like effect of initial concentration, effect of temperature, pH, and contact time were studied by batch method. The equilibrium data were best represented by the Langmuir isotherm model, and the maximum adsorption capacity of Cr(VI) onto biosorbent was found to be 19.68 mg/g. The pseudo-second-order kinetic model adequately described the kinetic data. The calculated values of thermodynamic parameters such as enthalpy change (?H ⁰), entropy change (?S ⁰), and free energy change (?G ⁰) were 21.55 kJ/mol, 76.24 J/mol?K, and ?1.55 kJ/mol, respectively, at 30 °C which accounted for spontaneous and endothermic processes. The study of adsorbent capacity for Cr(VI) removal in the presence of Na⁺, Mg²⁺, Ca²⁺, SO ₄ ^2? , HCO ₃ ^? and Cl^? illustrated that the removal of Cr(VI) increased in the presence of HCO^3? ions; the presence of Na⁺, SO ₄ ^2? or Cl^? showed no significant influence on Cr(VI) adsorption, while Ca²⁺ and Mg²⁺ ions led to an insignificant decrease in Cr(VI) adsorption. Further, the desorption studies illustrated that 31.10 % of metal ions can be removed from an aqueous system, out of which 26.63 % of metal ions can be recovered by desorption in first cycle and the adsorbent can be reused. The results of the scale-up study show that the ecofriendly detoxification of Cr(VI) from aqueous systems was technologically feasible.     

A field trial of nutrient stimulation of methanotrophs to reduce greenhouse gas emissions from landfill cover soils

Landfills are among the major sources of anthropogenic methane (CH₄) estimated to reach 40?×?10⁹kg per year worldwide by 2015 (IPCC, 2007 IPCC. 2007. Intergovernmental Panel on Climate Change, Synthesis Report on Contributions of Work Groups 1, 2, and 3 to the Fourth Assessment Report Core Writing Team, Edited by: Pauchar, R.K. and Reisinger, A. Geneva, Switzerland: IPCC.  [Google Scholar]). A 2½-year field experiment was conducted at a closed landfill in western Michigan where methanotrophs, methane-consuming bacteria, were stimulated by nutrient addition to the soil without significantly increasing biogenic nitrous oxide (N₂O) production. The effects of the nitrogen amendments (KNO₃ and NH₄Cl), phenylacetylene (a selective inhibitor of nitrifying bacteria that contribute to N₂O production), and a canopy (to reduce direct water infiltration) on the vertical soil gas profiles of CH₄, CO₂, and O₂ were measured in the top meter of the soil. Methane and nitrous oxide fluxes were calculated from the corresponding soil gas concentration gradients with respect to depth and a Millington–Quirk diffusivity coefficient in soil derived empirically from soil porosity, water content, and diffusivity coefficients in air from the literature. Methane flux estimates were as high as 218.4 g m^?2 day^?1 in the fall and 12.8 g/m^?2 day^?1 in the summer. During the spring and summer, CH₄ fluxes were reduced by more than half by adding KNO₃ and NH₄Cl into the soil as compared to control plots, while N₂O fluxes increased substantially. The concurrent addition of phenylacetylene to the amendment decreased peak N₂O production by half and the rate of peak methane oxidation by about one-third. The seasonal average methane and N₂O flux data were extrapolated to estimate the reduction of CH₄ and N₂O fluxes into the atmosphere by nitrogen and inhibitor addition to the cover soils. The results suggest that such additions coupled with soil moisture management may provide a potential strategy to significantly reduce greenhouse gas emissions from landfills.

Implications The results of a 2½-year study of effects of nutrient stimulation on methane oxidation in landfill cover soils demonstrates that nutrient addition does decrease methane emissions. The work further underscores the control which soil moisture exerts on methane oxidation. Water management is critical to the success of methane oxidation strategies.     

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.     

Acute and chronic toxicity of benzotriazoles to aquatic organisms

Purpose

Resulting from their intensive use as corrosion inhibitors in aircraft deicing and anti-icing fluids (ADAF) and for silver protection in dishwasher detergents benzotriazoles (BTs) are widespread in European surface waters. The current study aimed on an ecotoxicological characterization of 1H-benzotriazole (1H-BT) and 5-methyl-1H-benzotriazole (5MBT).

Methods

Acute and chronic OECD guideline tests were conducted with primary producers (Desmodesmus subspicatus, Lemna minor) and two daphnia species (Daphnia magna, Daphnia galeata) to characterize the hazard of these chemicals. Additionally, the estrogenic activity of both BTs was analyzed in vitro using a recombinant yeast estrogen screen (YES).

Results

Both BTs revealed significant effects in acute and chronic experiments, but exhibited no estrogenic activity in the YES. The algal growth test displayed an inhibited cell number increase with effect concentration (EC) values of EC₁₀ 1.18 and 2.86?mg?l^-1 for 1H-BT and 5MBT, respectively. In the Lemna test, EC₁₀ values were 3.94?mg?l^-1 (1H-BT) and 2.11?mg?l^-1 (5MBT). D. magna was also affected with EC₅₀ (48?h) values of 107?mg?l^-1 for 1H-BT and 51.6?mg?l^-1 for 5MBT. D. galeata was more sensitive with an EC₅₀ (48?h) of 14.7?mg 1H-BT l^-1 and 8.13?mg 5MBT l^-1. In the 21-day reproduction tests with D. magna, the EC₁₀ for 5MBT was 5.93?mg?l^-1 while 1H-BT showed no adverse effects. D. galeata turned out to be more sensitive in the chronic study with EC₁₀ values of 0.97?mg?l^-1 for 1H-BT and 0.40?mg?l^-1 for 5 MBT.

Conclusion

Because BTs are regularly found in the aquatic environment at lower ??g l^-1 concentrations reflecting their persistence and poor elimination during wastewater treatment processes, a preliminary risk assessment was conducted. There is little indication that BTs pose a risk for aquatic ecosystems at current exposure levels during most of the year. However, it cannot be excluded that in winter with a higher usage of ADAFs environmental concentrations may well exceed the level that is considered safe for aquatic organisms.     

Biosorption of antimony(V) by freshwater cyanobacteria Microcystis from Lake Taihu,China: effects of pH and competitive ions

There is limited knowledge available on metalloid biosorption by freshwater algae. In this study, biosorption properties of anionic Sb(OH) ₆ ^? by naturally occurring cyanobacteria Microcystis were investigated as a function of initial pH, biosorbent dosage, contact time, and addition sequences of competitive ions, and their binding mechanisms were discussed. The biosorption process was fast and equilibrium was reached at 2 h. Sb(V) biosorption decreased with the increase of pH and the optimum pH range was 2.5–3.0, which corresponded with the changes of surface charges of the cell wall of Microcystis. The biosorption data satisfactorily followed the Freundlich model. The simultaneous addition of H₂PO₄ ^? and Ca²⁺ enhanced Sb(V) biosorption, while NO₃ ^? greatly inhibited the biosorption, compared with single Sb(V) addition. The initial addition of the competitive ions reduced Sb(V) biosorption at higher Sb(V) concentrations, compared with simultaneous addition. A fraction of biosorbed Sb(V) was replaced by the competitive ions which were added subsequently, and the exchange only occurred at higher concentrations of Sb(V). 1.0 mol/L HCl demonstrated the highest desorption efficiency. Speciation analyses indicated that no reduction of Sb(V) into Sb(III) occurred. Based on the results of zeta potential and attenuated total reflection infrared spectroscopy spectra, Sb(OH) ₆ ^? bound to the biomass through electrostatic attraction and surface complexation, and amino, carboxyl, and hydroxyl groups were involved in the biosorption process. The study suggest that Microcystis from cyanobacteria blooms could be used as a potential biosorbent to remove Sb(V) from effluents at environmentally relevant concentrations (≤10.0 mg/L).     

Human health risk from organ-specific accumulation of toxic metals and response of antioxidants in edible fish species from Chenab River,Pakistan

In the current study, the bioaccumulation of essential and nonessential metals and related antioxidant activity were analyzed in three organs (muscle, gills, and liver) of herbivorous (HF) and carnivorous (CF) edible fish of Chenab River. The comparative analysis revealed a more heterogeneous accumulation of metals in the muscles of HF fish than that of CF fish [chromium (Cr, 3.4 μg g^?1), cobalt (Co, 1.7 μg g^?1), copper (Cu, 3 μg g^?1), and iron (Fe, 45 μg g^?1) versus Cr (1.3 μg g^?1), Co (0.1 μg g^?1), Cu (1.1 μg g^?1), and Fe (33 μg g^?1), respectively, P?<?0.001]. These results implied an organ-specific accumulation of metals at different trophic levels. According to logistic regression analysis, the bioaccumulation of metals had marked differences in HF and CF. The antioxidant activity was significantly related to the tissue type and the metals to which the organs are exposed to. The liver of CF fish had a higher activity of antioxidant superoxide dismutase (SOD), catalase (CAT), glutathione (GSH), and lipid peroxidase (LPO) than that of HF (P?<?0.05). LPO and guaiacol peroxidase (POD) in both groups were associated with a number of metals, but in HF, cadmium (Cd), Cr, Pb, and Zn were more related with the LPO and SOD activities. Moreover, Cd, Co, Fe, Pb, Ni, Cu, and Zn were above the permissible limits set by various agencies. In numerous cases, our results were even higher than those previously reported in the literature. The results provide an insight into the pollution pattern of Chenab River. These results may be helpful in the future to identify biomarkers of exposure in aquatic organisms.

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.