Release of vanadium from oxidized sediments: insights from different extraction and leaching procedures

Although the attention for vanadium (V) as a potentially harmful element is growing and some countries adopted threshold values for V in soils, sediments, groundwater, or surface water, V is generally of little importance in environmental legislation and the knowledge about the behavior of V in the environment is still limited. In the present study, the release of V from oxidized sediments, sediment-derived soils, and certified reference materials was investigated by means of several types of leaching tests and extractions that are frequently used for soil and sediment characterization. The pH_stat leaching tests and single and sequential extractions applied in this study show that V generally displays a very limited actual and potential mobility in sediment. “Mobile” V concentrations, as estimated by the amount of V released by a single extraction with CaCl₂ 0.01 mol L^?1, were low, even in the most contaminated sediment samples. Only under strongly acidifying conditions (pH 2), such as in the case of ingestion of soil or sediment or in accidental spills, a substantial release of V can be expected.     

Research and application of method of oxygen isotope of inorganic phosphate in Beijing agricultural soils

Phosphorus (P) in agricultural ecosystems is an essential and limited element for plants and microorganisms. However, environmental problems caused by P accumulation as well as by P loss have become more and more serious. Oxygen isotopes of phosphate can trace the sources, migration, and transformation of P in agricultural soils. In order to use the isotopes of phosphate oxygen, appropriate extraction and purification methods for inorganic phosphate from soils are necessary. Here, we combined two different methods to analyze the oxygen isotopic composition of inorganic phosphate (δ¹⁸O_P) from chemical fertilizers and different fractions (Milli-Q water, 0.5 mol L^?1 NaHCO₃ (pH = 8.5), 0.1 mol L^?1 NaOH and 1 mol L^?1 HCl) of agricultural soils from the Beijing area. The δ¹⁸O_P results of the water extracts and NaHCO₃ extracts in most samples were close to the calculated equilibrium value. These phenomena can be explained by rapid P cycling in soils and the influence of chemical fertilizers. The δ¹⁸O_P value of the water extracts and NaHCO₃ extracts in some soil samples below the equilibrium value may be caused by the hydrolysis of organic P fractions mediated by extracellular enzymes. The δ¹⁸O_P values of the NaOH extracts were above the calculated equilibrium value reflecting the balance state between microbial uptake of phosphate and the release of intracellular phosphate back to the soil. The HCl extracts with the lowest δ¹⁸O_P values and highest phosphate concentrations indicated that the HCl fraction was affected by microbial activity. Hence, these δ¹⁸O_p values likely reflected the oxygen isotopic values of the parent materials. The results suggested that phosphate oxygen isotope analyses could be an effective tool in order to trace phosphate sources, transformation processes, and its utilization by microorganisms in agricultural soils.     

Remediation of acid mine drainage (AMD)-contaminated soil by Phragmites australis and rhizosphere bacteria

Experiments were conducted to assess the impact of citric acid (CA) and rhizosphere bacteria on metal uptake in Phragmites australis cultured in a spiked acid mine drainage (AMD) soil. Rhizosphere iron-oxidizing bacteria (Fe(II)OB) enhanced the formation of Fe plaque on roots, which decreased the uptake of Fe and Mn. CA inhibited the growth of Fe(II)OB, decreased the formation of metal plaque, raised the metal mobility in soil, and increased the accumulation of metals in all tissues of the reeds. The higher the CA dosage, the more metals accumulated into reeds. The total amount of metals in reeds increased from 7.8?±?0.5?×?10^?6 mol plant^?1 (Mn), 1.4?±?0.1?×?10^?3 mol plant^?1 (Fe), and 1.0?±?0.1?×?10^?4 mol plant^?1 (Al) in spiked soil without CA to 22.2?±?0.5?×?10^?6 mol plant^?1 (Mn), 3.5?±?0.06?×?10^?3 mol plant^?1 (Fe), and 5.0?±?0.2?×?10^?4 mol plant^?1 (Al) in soil added with 33.616 g C₆H₈O₇·H₂O for per kilogram soil. CA could be effective at enhancing the phytoremediation of metals from AMD-contaminated soil.     

Impact of lime-stabilized biosolid application on Cu,Ni, Pb and Zn mobility in an acidic soil

A soil column leaching study was conducted on an acidic soil in order to assess the impact of lime-stabilized biosolid on the mobility of metallic pollutants (Cu, Ni, Pb and Zn). Column leaching experiments were conducted by injecting successively CaCl₂, oxalic acid and ethylenediaminetetraacetic acid (EDTA) solutions through soil and biosolid-amended soil columns. The comparison of leaching curves showed that the transport of metals is mainly related to the dissolved organic carbon, pH and the nature of extractants. Metal mobility in the soil and biosolid-amended soils is higher with EDTA than with CaCl₂ and oxalic acid extractions, indicating that metals are strongly bound to solid-phase components. The single application of lime-stabilized biosolid at a rate ranging from 15 to 30 t/ha tends to decrease the mobility of metals, while repeated applications (2?×?15 t/ha) increase metal leaching from soil. This result highlights the importance of monitoring the movement and concentrations of metals, especially in acid and sandy soils with shallow and smaller water bodies.     

Extraction of Sudan dyes from environmental water by hemimicelles-based magnetic titanium dioxide nanoparticles

A novel method for the extraction of Sudan dyes including Sudan I, II, III, and IV from environmental water by magnetic titanium dioxide nanoparticles (Fe₃O₄@TiO₂) coated with sodium dodecylsulfate (SDS) as adsorbent was reported. Fe₃O₄@TiO₂ was synthesized by a simple method and was characterized by transmission electron microscopy, Fourier-transform infrared spectrometry, and vibrating sample magnetometer. The magnetic separation was quite efficient for the adsorption and desorption of Sudan dyes. The effect of the amount of SDS, extraction time, pH, desorption condition, maximal extraction volume, and humic acid on the extraction process were investigated. This method was employed to analyze three environmental water samples. The results demonstrated that our proposed method had wide linear range (25–5,000 ng L^?1) with a good linearity (R ²?>?0.999) and low detection limits (2.9–7.3 ng L^?1). An enrichment factor of 1,000 was achieved. In all three spiked levels (25, 250, and 2,500 ng L^?1), the recoveries of Sudan dyes were in the range of 86.9–93.6 %. The relative standard deviations obtained were ranging from 2.5 to 9.3 %. That is to say, the new method was fast and effective for the extraction of Sudan dye from environmental water.     

Accumulation and spatial distribution of Cd, Cr, and Pb in mulberry from municipal solid waste compost following application of EDTA and (NH4)2SO4

Municipal solid waste compost can be used to cropland as soil amendment to supply nutrients and improve soil physical properties. But long-term application of municipal solid waste (MSW) compost may result in accumulation of toxic metals in amended soil. Phytoremediation, especially phytoextraction, is a novel, cost-effective, and environmentally friendly approach that uses metal-accumulating plants to concentrate and remove metals from contaminated soils. Ethylenediaminetetraacetate (EDTA) was applied to metal-contaminated soil to increase the mobility and phytoavailability of metals in soil, thereby increasing the amount of toxic metals accumulated in the upper parts of phytoextracting plants. The objectives of this study were (1) to investigate the accumulation and spatial distribution of toxic metals (Cd, Cr, and Pb) in mulberry from MSW compost with the application of EDTA and (NH₄)₂SO₄, (2) to examine the effectiveness of EDTA and (NH₄)₂SO₄ applied together on toxic metals (Cd, Cr, and Pb) removal by mulberry under field conditions, and (3) to evaluate the potential of mulberry for phytoextraction of toxic metals from MSW compost. The tested plant—mulberry had been grown in MSW compost field for 4 years. EDTA solution at five rates (0, 50, 100, 50 mmol L^?1?+?1 g?L^?1 (NH₄)₂SO₄, and 100 mmol L^?1?+?1 g?L^?1 (NH₄)₂SO₄) was added into mulberry root medium in September 2009. Twenty days later, the plants were harvested and separated into six parts according to plant height. Cd, Cr, and Pb contents in plant samples and MSW compost were analyzed using an atomic absorption spectrophotometer. In the same treatment, Cd, Cr, and Pb concentrations in mulberry shoot were all higher than those in root, and Cd and Pb concentrations in shoot increased from lower to upper parts, reaching the highest in leaves. Significant increases were found in toxic metal concentration in different parts of mulberry with increasing EDTA concentration, especially when combined with (NH₄)₂SO₄. Mulberry exhibited high ability to accumulate Cd with bioconcentration factors (BCFs) higher than 1. EDTA application also significantly increased Cd BCFs. More than 30 % of metal uptake was concentrated in mulberry branches (stem of above 100 cm height) and leaves. Results presented here show that mulberry is a woody plant that has the potential of Cd phytoextraction from MSW compost by removing leaves and cutting branches. The application of EDTA combined with (NH₄)₂SO₄ significantly enhanced the efficiency of mulberry in removing Cd from the compost medium. Adding (NH₄)₂SO₄ into the compost will lower the risk of the exposure of environment to excessive non-biodegradable EDTA in a large-scale EDTA-assisted phytoextraction by reducing the dosage of EDTA. In China, the need for sod is increasing day by day. Sod is often produced on arable soil and sold together with soils. This would lead to the soil being infertile and the soil layer thin. After several times’ production, the soil can no longer be used for cultivating crops and be destroyed. In order to fully utilize MSW compost resources and save valuable soil resources, MSW compost can be used to replace arable soil to produce sod after extraction of toxic metals in it.     

High-performance liquid chromatography (HPLC) as a tool for monitoring the fate of fluazinam in soil

Fluazinam is a widely used pesticide employed against the fungal disease late blight in potato cultivation. A specific, repeatable, and rapid high-performance liquid chromatography (HPLC) method utilizing a diode array detector (DAD) was developed to determine the presence of fluazinam in soil. The method consists of acetonitrile (ACN) extraction, clean-up with solid-phase extraction (SPE), and separation using a mobile phase consisting of 70% ACN and 30% water (v/v), including 0.02% acetic acid. HPLC was performed with a C18 column and the detection wavelength was 240 nm. The method was successfully applied to an incubation experiment and to soil samples taken from potato fields where fluazinam had been applied two to three times during the on-going growing season. In the 90-day incubation experiment, analytical standard fluazinam and the commercial fungicide Shirlan^® were added to soil samples that had never been treated with fluazinam, and were then extracted with ACN and 0.01 M calcium chloride (CaCl₂). Fluazinam was not extractable with CaCl₂, indicating that it does not leach to watercourses in the dissolved form. Recovery with ACN extraction for sandy soils was 72–95% immediately after application and 53–73% after 90 days of incubation. Out of the eight potato field soil samples, fluazinam was found in two samples at concentrations of 2.1 mg kg^?1 and 1.9 mg kg^?1, well above the limit of quantification (0.1 mg kg^?1).     

Degradation of ethylenethiourea pesticide metabolite from water by photocatalytic processes

In this study, photocatalytic (photo-Fenton and H₂O₂/UV) and dark Fenton processes were used to remove ethylenethiourea (ETU) from water. The experiments were conducted in a photo-reactor with an 80 W mercury vapor lamp. The mineralization of ETU was determined by total organic carbon analysis, and ETU degradation was qualitatively monitored by the reduction of UV absorbance at 232 nm. A higher mineralization efficiency was obtained by using the photo-peroxidation process (UV/H₂O₂). Approximately 77% of ETU was mineralized within 120 min of the reaction using [H₂O₂]₀ = 400 mg L^?1. The photo-Fenton process mineralized 70% of the ETU with [H₂O₂]₀ = 800 mg L^?1 and [Fe²⁺] = 400 mg L^?1, and there is evidence that hydrogen peroxide was the limiting reagent in the reaction because it was rapidly consumed. Moreover, increasing the concentration of H₂O₂ from 800 mg L^?1 to 1200 mg L^?1 did not enhance the degradation of ETU. Kinetics studies revealed that the pseudo-second-order model best fit the experimental conditions. The k values for the UV/H₂O₂ and photo-Fenton processes were determined to be 6.2 × 10^?4 mg L^?1 min^?1 and 7.7 × 10^?4 mg L^?1 min^?1, respectively. The mineralization of ETU in the absence of hydrogen peroxide has led to the conclusion that ETU transformation products are susceptible to photolysis by UV light. These are promising results for further research. The processes that were investigated can be used to remove pesticide metabolites from drinking water sources and wastewater in developing countries.     

Environmental effects of anticholinesterasic therapeutic drugs on a crustacean species,Daphnia magna

The presence of pharmaceutical drugs in the environment is an important field of toxicology, since such residues can cause deleterious effects on exposed biota. This study assessed the ecotoxicological acute and chronic effects of two anticholinesterasic drugs, neostigmine and pyridostigmine in Daphnia magna. Our study calculated 48 h-EC₅₀ values for the immobilization assay of 167.7 μg L^?1 for neostigmine and 91.3 μg L^?1 for pyridostigmine. In terms of feeding behavior, we calculated a 5 h-EC₅₀ for filtration rates of 7.1 and 0.2 μg L^?1 for neostigmine and pyridostigmine, respectively; for the ingestion rates, the calculated EC₅₀ values were, respectively, 7.5 and 0.2 μg L^?1 for neostigmine and pyridostigmine. In the reproduction assay, the most affected parameter was the somatic growth rate (LOECs of 21.0 and 2.9 μg L^?1 for neostigmine and pyridostigmine, respectively), followed by the fecundity (LOECs of 41.9 and 11.4 μg L^?1 for neostigmine and pyridostigmine, respectively). We also determined a 48 h-IC₅₀ for cholinesterase activity of 1.7 and 4.5 μg L^?1 for neostigmine and pyridostigmine, respectively. These results demonstrated that both compounds are potentially toxic for D. magna at concentrations in the order of the μg L^?1.     

Facile, effective, and environment-friendly degradation of sulfamonomethoxine in aqueous solution with the aid of a UV/Oxone oxidative process

The degradation of sulfamonomethoxine (SMM) in the aqueous environment by the combination of UV illumination and Oxone has been studied. Experimental results indicated that the UV illumination can effectively activate Oxone to produce sulfate-free radicals (SO₄ ^??). When 10 mmol L^?1 Oxone was added, 96.78 % removal of SMM (5 mg L^?1) was achieved within 90 min. Mineralization of SMM was investigated by measuring the total organic carbon, which decreased by 89.01 % after 90 min reaction. Six intermediate compounds generated during the SMM degradation were identified with the aid of liquid chromatography and mass spectroscopy, combined with proton nuclear magnetic resonance spectroscopy. A general reaction pathway for the degradation of SMM was proposed, where the presence of SO₄ ^?? remained crucial during the degradation process.     

Methane biofiltration in the presence of ethanol vapor under steady and transient state conditions: an experimental study

Methane (CH₄) removal in the presence of ethanol vapors was performed by a stone-based bed and a hybrid packing biofilter in parallel. In the absence of ethanol, a methane removal efficiency of 55 ± 1% was obtained for both biofilters under similar CH₄ inlet load (IL) of 13 ± 0.5 g_CH4 m^?3 h^?1 and an empty bed residence time (EBRT) of 6 min. The results proved the key role of the bottom section in both biofilters for simultaneous removal of CH₄ and ethanol. Ethanol vapor was completely eliminated in the bottom sections for an ethanol IL variation between 1 and 11 g_ethanol m^?3 h^?1. Ethanol absorption and accumulation in the biofilm phase as well as ethanol conversion to CO₂ contributed to ethanol removal efficiency of 100%. In the presence of ethanol vapor, CO₂ productions in the bottom section increased almost fourfold in both biofilters. The ethanol concentration in the leachate of the biofilter exceeding 2200 g_ethanol m^?3 _leachate in both biofilters demonstrated the excess accumulation of ethanol in the biofilm phase. The biofilters responded quickly to an ethanol shock load followed by a starvation with 20% decrease of their performance. The return to normal operations in both biofilters after the transient conditions took less than 5 days. Unlike the hybrid packing biofilter, excess pressure drop (up to 1.9 cmH₂O m^?1) was an important concern for the stone bed biofilter. The biomass accumulation in the bottom section of the stone bed biofilter contributed to 80% of the total pressure drop. However, the 14-day starvation reduced the pressure drop to 0.25 cmH₂O m^?1.     

Single and combined effects of aluminum (Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) and zinc (ZnO) oxide nanoparticles in a freshwater fish, <Emphasis Type="Italic">Carassius auratus</Emphasis>

The increasing use of nanoparticles (NPs) worldwide has raised some concerns about their impact on the environment. The aim of the study was to assess the toxicity of metal oxide nanoparticles, singly or combined, in a freshwater fish (Carassius auratus). The fish were exposed for 7, 14, and 21 days to different concentrations of NPs (10 μg Al₂O₃.L^?1, 10 μg ZnO.L^?1, 10 μg Al₂O₃.L^?1 plus 10 μg ZnO.L^?1, 100 μg Al₂O₃.L^?1, 100 μg ZnO.L^?1, and 100 μg Al₂O₃.L^?1 plus 100 μg ZnO.L^?1). At the end of each exposure period, antioxidant enzyme activity (catalase, glutathione-S-transferase, and superoxide dismutase), lipid peroxidation, and histopathology were assessed in the gills and livers of C. auratus. The results show an increase in catalase (CAT) and superoxide dismutase (SOD) activity in the gills and livers of fish, especially after 14 days of exposure to single and combined NPs, followed by a reduction at 21 days. An increase in glutathione S-transferase (GST) was observed in gills after 7 days for all tested NP concentrations (single and combined); while in livers, a significant increase was determined after 14 days of exposure to 100 μg.L^?1 of both single ZnO and Al₂O₃ NPs. Lipid peroxidation (LPO) significantly increased in gills after 7 days of exposure to 100 μg.L^?1 Al₂O₃ NPs (single or combined). In livers, LPO increased significantly after 7 days of exposure to all tested concentrations of both single ZnO and Al₂O₃ (except for 10 μg Al₂O₃.L^?1), and after 14 days of exposure to ZnO (10 and 100 μg.L^?1) and Al₂O₃ (100 μg.L^?1)_. The results from histological observations suggest that exposure to metal oxide NPs affected both livers and gills, presenting alterations such as gill hyperplasia and liver degeneration. However, the most pronounced effects were found in gills. In general, this study shows that the tested NPs, single or combined, are capable of causing sub-lethal effects on C. auratus, but when combined, NPs seem to be slightly more toxic than when added alone.     

A study on As, Cu, Pb and Zn (bio)availability in an abandoned mine area (São Domingos, Portugal) using chemical and ecotoxicological tools

The aim of this study was to relate the results obtained by chemical methods, used to assess environmental (bio)availability, with the ecotoxic response and bioaccumulation of trace elements (TE) by the earthworm Eisenia fetida exposed to field-contaminated, metal-polluted soils from a sulphide mine. The extracting solution 0.5 M NH₄CH₃COO, 0.5 M CH₃COOH and 0.02 M EDTA (pH 4.7), was able to predict environmental bioavailability of TE to E. fetida. However, the toxicological bioavailability could not be predicted from the results of the chemical extractions or from the bioaccumulation results: E. fetida reproduction was higher in soils where environmental bioavailability of TE and bioaccumulation values were also higher. In this study, the toxic response of the organism seemed to be more influenced by the overall nutritional status of the soil (e.g. pH, organic matter, plant nutrient availability and cation exchange capacity) than by its TE contamination. In the case of anthropogenic multi-contaminated sites, the different soil characteristics exert an important and confounding influence in the toxic response and the relationship between different bioavailable fractions cannot be easily established, emphasising the need to combine results from chemical methods with those from bioassays when evaluating the bioavailability of TE in these soils.     

FTIR gas-phase kinetic study on the reactions of some acrylate esters with OH radicals and Cl atoms

Acrylate esters are α,β-unsaturated esters that contain vinyl groups directly attached to the carbonyl carbon. These compounds are widely used in the production of plastics and resins. Atmospheric degradation processes of these compounds are currently not well understood. The kinetics of the gas phase reactions of OH radicals with methyl 3-methylacrylate and methyl 3,3-dimethylacrylate were determined using the relative rate technique in a 50 L Pyrex photoreactor using in situ FTIR spectroscopy at room temperature (298?±?2 K) and atmospheric pressure (708?±?8 Torr) with air as the bath gas. Rate coefficients obtained were (in units cm³ molecule^?1 s^?1): (3.27?±?0.33)?×?10^?11 and (4.43?±?0.42)?×?10^?11, for CH₃CH═CHC(O)OCH₃ and (CH₃)₂CH═CHC(O)OCH_3, respectively. The same technique was used to study the gas phase reactions of hexyl acrylate and ethyl hexyl acrylate with OH radicals and Cl atoms. In the experiments with Cl, N₂ and air were used as the bath gases. The following rate coefficients were obtained (in cm³ molecule^?1 s^?1): k₃ (CH₂═CHC(O)O(CH₂)₅CH₃?+?Cl)?=?(3.31?±?0.31)?×?10^?10, k₄(CH₂═CHC(O)OCH₂CH(CH₂CH₃)(CH₂)₃CH₃?+?Cl)?=?(3.46?±?0.31)?×?10^?10, k₅(CH₂═CHC(O)O(CH₂)₅CH₃?+?OH)?=?(2.28?±?0.23)?×?10^?11, and k₆(CH₂═CHC(O)OCH₂CH(CH₂CH₃)(CH₂)₃CH₃?+?OH)?=?(2.74?±?0.26)?×?10^?11. The reactivity increased with the number of methyl substituents on the double bond and with the chain length of the alkyl group in –C(O)OR. Estimations of the atmospheric lifetimes clearly indicate that the dominant atmospheric loss process for these compounds is their daytime reaction with the hydroxyl radical. In coastal areas and in some polluted environments, Cl atom-initiated degradation of these compounds can be significant, if not dominant. Maximum Incremental Reactivity (MIR) index and global warming potential (GWP) were also calculated, and it was concluded that these compounds have significant MIR values, but they do not influence global warming.     

The capability of estuarine sediments to remove nitrogen: implications for drinking water resource in Yangtze Estuary

Water in the Yangtze Estuary is fresh most of the year because of the large discharge of Yangtze River. The Qingcaosha Reservoir built on the Changxing Island in the Yangtze Estuary is an estuarine reservoir for drinking water. Denitrification rate in the top 10 cm sediment of the intertidal marshes and bare mudflat of Yangtze Estuarine islands was measured by the acetylene inhibition method. Annual denitrification rate in the top 10 cm of sediment was 23.1 μmol m^?2 h^?1 in marshes (ranged from 7.5 to 42.1 μmol m^?2 h^?1) and 15.1 μmol m^?2 h^?1 at the mudflat (ranged from 6.6 to 26.5 μmol m^?2 h^?1). Annual average denitrification rate is higher at mashes than at mudflat, but without a significant difference (p?=?0.084, paired t test.). Taking into account the vegetation and water area of the reservoir, a total 1.42?×?10⁸ g N could be converted into nitrogen gas (N₂) annually by the sediment, which is 97.7 % of the dissolved inorganic nitrogen input through precipitation. Denitrification in reservoir sediment can control the bioavailable nitrogen level of the water body. At the Yangtze estuary, denitrification primarily took place in the top 4 cm of sediment, and there was no significant spatial or temporal variation of denitrification during the year at the marshes and mudflat, which led to no single factor determining the denitrification process but the combined effects of the environmental factors, hydrologic condition, and wetland vegetation.     

A new strategy for determination of hydroxylamine and phenol in water and waste water samples using modified nanosensor

A carbon paste electrode modified with p-chloranil and carbon nanotubes was used for the sensitive and selective voltammetric determination of hydroxylamine (HX) and phenol (PL). The oxidation of HX at the modified electrode was investigated by cyclic voltammetry (CV), chronoamperommetry, and electrochemical impedance spectroscopy. The values of the catalytic rate constant (k), and diffusion coefficient (D) for HX were calculated. Square wave voltammetric peaks current of HX and PL increased linearly with their concentrations at the ranges of 0.1–172.0 and 5.0–512.0 μmol L^?1, respectively. The detection limits for HX and PL were 0.08 and 2.0 μmol L^?1, respectively. The separation of the anodic peak potentials of HX and PL reached to 0.65 V, using square wave voltammetry. The proposed sensor was successfully applied for the determination of HX and PL in water and wastewater samples.     

Insights into real cotton-textile dyeing wastewater treatment using solar advanced oxidation processes

Different advanced oxidation processes (AOPs) were applied to the treatment of a real cotton-textile dyeing wastewater as a pre-oxidation step to enhance the biodegradability of the recalcitrant compounds, which can be further oxidized using a biological process. Tests were conducted on a lab-scale prototype using artificial solar radiation and at pilot scale with compound parabolic collectors using natural solar radiation. The cotton-textile dyeing wastewater presents a lilac color, with a maximum absorbance peak at 641 nm, alkaline pH (pH?=?8.2), moderate organic content (DOC?=?152 mg C L^?1, COD?=?684 mg O₂ L^?1) and low-moderate biodegradability (40 % after 28 days in Zahn–Wellens test). All the tested processes contributed to an effective decolorization and mineralization, but the most efficient process was the solar-photo-Fenton with an optimum catalyst concentration of 60 mg Fe²⁺ L^?1, leading to 98.5 % decolorization and 85.5 % mineralization after less than 0.1 and 5.8 kJ_UV L^?1, respectively. In order to achieve a final wastewater with a COD below 250 mg O₂ L^?1 (discharge limit into water bodies imposed by the Portuguese Legislation-Portaria no. 423/97 of 25 June 1997), considering the combination of a solar-photo-Fenton reaction with a biological process, the phototreatment energy required is 0.5 kJ_UV L^?1, consuming 7.5 mM hydrogen peroxide, resulting in 58.4 % of mineralization $ \left({t}_{30\mathrm{W}}=3.2\ \min; \overline{T}=30.7\ {}^{\circ}\mathrm{C};\overline{\mathrm{pH}}=2.80;{\overline{\mathrm{UV}}}_{G,n}={13\ \mathrm{W}\ \mathrm{m}}^{-2}\right). $      

Effects of nitrogen application rate and a nitrification inhibitor dicyandiamide on methanotroph abundance and methane uptake in a grazed pasture soil

Methane-oxidizing bacteria (methanotrophs) in the soil are a unique group of methylotrophic bacteria that utilize methane (CH₄) as their sole source of carbon and energy which limit the flux of methane to the atmosphere from soils and consume atmospheric methane. A field experiment was conducted to determine the effect of nitrogen application rates and the nitrification inhibitor dicyandiamide (DCD) on the abundance of methanotrophs and on methane flux in a grazed pasture soil. Nitrogen (N) was applied at four different rates, with urea applied at 50 and 100 kg N ha^?1 and animal urine at 300 and 600 kg N ha^?1. DCD was applied at 10 kg ha^?1. The results showed that both the DNA and selected mRNA copy numbers of the methanotroph pmoA gene were not affected by the application of urea, urine or DCD. The methanotroph DNA and mRNA pmoA gene copy numbers were low in this soil, below 7.13?×?10³ g^?1 soil and 3.75?×?10³ μg^?1 RNA, respectively. Daily CH₄ flux varied slightly among different treatments during the experimental period, ranging from ?12.89 g CH₄ ha^?1 day^?1 to ?0.83 g CH₄ ha^?1 day^?1, but no significant treatment effect was found. This study suggests that the application of urea fertilizer, animal urine returns and the use of the nitrification inhibitor DCD do not significantly affect soil methanotroph abundance or daily CH₄ fluxes in grazed grassland soils.     

Acute toxicity and ecotoxicological risk assessment of rice pesticides to Lithobates catesbeianus tadpoles

The objective of this study was to determine the acute toxicity of some pesticides used in irrigated rice farming to Lithobates catesbeianus tadpoles. The LC_50-96h for commercial formulations containing bentazon, penoxsulam, vegetable oil, permethrin and carbofuran, separately and their mixtures, were determined at the proportions commonly used in the field. The limits of risk concentrations of these products for the studied species were also established. The LC_50-96h for tadpoles was 4,530 mg L^?1 for bentazon; 7.52 mg L^?1 for penoxsulam + 145.66 mg L^?1 of vegetable oil; 81.57 mg L^?1 for vegetable oil; 0.10 mg L^?1 for permethrin; 29.90 mg L^?1 for carbofuran (active ingredients), and 38.79 times the dose used in the field for the mixture of these products. The environmental risk was determined only for permethrin, and care should be taken when using the vegetable oil.     

Determination of phenols and pharmaceuticals in municipal wastewaters from Polish treatment plants by ultrasound-assisted emulsification–microextraction followed by GC–MS

A method combining ultrasound-assisted emulsification–microextraction (USAEME) with gas chromatography–mass spectrometry (GC–MS) was developed for simultaneous determination of four acidic pharmaceuticals, ibuprofen, naproxen, ketoprofen, and diclofenac, as well as four phenols, 4-octylphenol, 4-n-nonylphenol, bisphenol A, and triclosan in municipal wastewaters. Conditions of extraction and simultaneous derivatization were optimized with respect to such aspects as type and volume of extraction solvent, volume of derivatization reagent, kind and amount of buffering salt, location of the test tube in the ultrasonic bath, and extraction time. The average correlation coefficient of the calibration curves was 0.9946. The LOD/(LOQ) values in influent and effluent wastewater were in the range of 0.002–0.121/(0.005–0.403) μg L^?1 and 0.002–0.828/(0.006–2.758) μg L^?1, respectively. Quantitative recoveries (≥94 %) and satisfactory precision (average RSD 8.2 %) were obtained. The optimized USAEME/GC–MS method was applied for determination of the considered pharmaceuticals and phenols in influents and treated effluents from nine Polish municipal wastewater treatment plants. The average concentration of acidic pharmaceuticals in influent and effluent wastewater were in the range of 0.06–551.96 μg L^?1 and 0.01–22.61 μg L^?1, respectively, while for phenols were in the range of 0.03–102.54 μg L^?1 and 0.02–10.84 μg L^?1, respectively. The removal efficiencies of the target compounds during purification process were between 84 and 99 %.