Optimizing pyrolysis temperature of contaminated rice straw biochar: Heavy metal(loid) deportment,properties evolution,and Pb adsorption/immobilization

Pyrolysis of rice straw (RS), a popular method for producing biochar, effectively treats heavy metal(loid)-contaminated RS. Here, we carried out this process at different temperatures and investigated the deportment of heavy metal(loid)s and the property evolution of biochars. Also, the optimal pyrolysis temperature for Pb adsorption and immobilization was studied. We observed that increasing the temperature could volatilize the heavy metal(loid)s. Cd was the most volatile metal therein, followed by As, while Ni, Cu, and Pb were relatively refractory. More than 75% of the remaining heavy metal(loid)s were non-exchangeable fractions at 700 °C, significantly reducing the environmental risk during subsequent application. Meanwhile, higher pyrolysis temperature resulted in higher pH values, higher surface areas, and stronger Pb adsorption capacity of RS biochars. The maximum adsorption capacity (Q_m) of biochars was in the order of BC300 (77.2 mg·g^?1) < BC500 (137.2 mg·g^?1) < BC700 (222.6 mg·g^?1). Besides, high-temperature biochar could significantly reduce the vertical Pb migration. And BC700 increased the fraction of residual Pb from 39.7% to 44.0% in the soil under the acid rain leaching condition. Therefore, we propose that the heavy metal(loid)-contaminated RS biochar produced at 700 °C might be more suitable for the remediation of soil heavily polluted in the Pb-smelting area.     

Persistence of fungitoxicity of two triorganotin(IV) compounds in soil

The persistence of triphenyltin chloride-triphenylphosphine oxide (Ph₃SnCl·Ph₃PO) and diphenylbutyltin bromide (Ph₂BuSnBr) in unsterilized sandy loam soil maintained in the dark at 60% of its water-holding capacity and at 27±2°C was studied over a period of 29 days. The percentage recovery of the compounds upon extraction with acetone immediately after application to soil was 60% for Ph₃SnCl·Ph₃PO and 9.8% for Ph₂BuSnBr. The half-lives of the compounds were 15 days for Ph₃SnCl·Ph₃PO and 14.2 days for Ph₂BuSnBr. After 29 days following application of the compounds in soil < 8.3 μg g^?1 of Ph₃SnCl·Ph₃PO and < 5.1 μg g^?1 of Ph₂BuSnBr remained in soil compared with the starting concentration of 50 μg of each compound per gram soil. The two triorganotin compounds were evidently easily degraded and the compounds may be applied every 2–3 weeks in the field at a rate of at least 0.005–0.01 kg ha^?1.     

QuEChERS and solid phase extraction methods for the determination of energy crop pesticides in soil,plant and runoff water matrices

QuEChERS and solid phase extraction (SPE) methods were applied for determining four herbicides (metazachlor, oxyfluorfen, quizalofop-p-ethyl, quinmerac) and one insecticide (α(±)-cypermethrin) in runoff water, soil, sunflower and oilseed rape plant matrices. Determination was performed using gas chromatography mass spectrometry (GC-MS), whereas high-pressure liquid chromatography mass spectrometry (HPLC-MS) was used for quinmerac. In all substrates linearity was evaluated using matrix-matched calibration samples at five concentration levels (50–1000 ng L^?1 for water, 5–500 μg kg^?1 for soil and 2.5–500 μg kg^?1 for sunflower or oilseed rape plant). Correlation coefficient was higher than 0.992 for all pesticides in all substrates. Acceptable mean recovery values were obtained for all pesticides in water (65.4–108.8%), soil (70.0–110.0%) and plant (66.1–118.6%), with intra- and inter-day RSD% below 20%. LODs were in the range of 0.250–26.6 ng L^?1 for water, 0.10–1.8 μg kg^?1 for soil and 0.15–2.0 μg kg^?1 for plants. The methods can be efficiently applied for field dissipation studies of the pesticides in energy crop cultivations.     

Occurrence of synthetic hormones in sewage effluents and Langat River and its tributaries,Malaysia

This study investigated for the first time the occurrence of selected synthetic hormones including 17α-ethinylestradiol, levonorgestrel, norethindrone and cyproterone acetate in Malaysian tropical waters. Samples were collected from the effluents of five sewage treatment plants (STPs) and at seven stations along the Langat River in Selangor, Malaysia, and its main tributaries. Samples were extracted by solid phase extraction (SPE) and analyzed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). In Langat river samples, only levonorgestrel and cyproterone acetate were found at 50% and 3.3% frequency. The concentrations detected for levonorgestrel ranged from less than the method detection limit (<MDL) to 213?ng?L^?1 and from?<?MDL to 76?ng?L^?1 for cyproterone acetate. For the STP effluent samples, levonorgestrel was <MDL in all samples and the concentrations detected were in the range?<?MDL – 262?ng?L^?1 for cyproterone acetate,?<?MDL ?11336?ng?L^?1 for norethindrone and?<?MDL – 1898?ng?L^?1 for 17α-ethinylestradiol.     

Extraction and Spectrophotometric Determination of Arsenic in the Environment

Abstract

A simple, sensitive and selective method for the determination of microamounts of arsenic (III) in the environment is described. Arsenic forms a yellow coloured complex with N-phenylbenzo-hydroxamic acid (PBHA) at pH 4.5-5.2 which can be extracted from chloroform. The effective molar absorptivity of As-PBHA extract is 1.1 × 1mol^?1cm^?1 at 410 nm. Many common ions associated with arsenic do not interfere. The effect of pH, reagent concentration and solvent is described. The arsenic in trace quantities is estimated in the industrial effluents, soil and glass samples.     

SPE–LC Multi-Residue Analysis of Mebendazole and its Metabolites in Grass Carp and Shrimp

An analytical method was developed to detect the residue of mebendazole and its metabolites (hydroxymebendazole and aminomebendazole) in the muscle of grass carp and shrimp by LC–UV detection. Mebendazole and its metabolites were extracted with water and ethyl acetate, defatted with hexane, and purified with MCX solid phase extraction column. The intra- and inter-batch precision (measured by CV%) was <9.0%. The accuracy (measured by relative error, %) was <12%. The LODs were 2.5 μg kg^?1 for mebendazole and hydroxymebendazole, 5 μg kg^?1 for aminomebendazole; the LOQs were 5 μg kg^?1 for mebendazole and hydroxymebendazole, 10 μg kg^?1 for aminomebendazole. The mean recoveries of mebendazole and its metabolites from grass carp and shrimp muscle at a concentration range of 5.0–500.0 μg kg^?1 were 90.7–97.0% with relative standard deviations below 10%.     

Simultaneous Degradation of Aqueous Trichloroacetic Acid by the Combined Action of Anodic Contact Glow Discharge Electrolysis and Normal Electrolytic Processes at the Cathode

To enhance the removal of trichloroacetic acid (TCA) by anodic contact glow discharge electrolysis (CGDE), the combined degradation of TCA by the action of anodic CGDE, denoted anodic degradation, and normal electrolytic processes at the cathode, denoted cathodic degradation, was investigated. Here, this overall process is termed simultaneous degradation. Compared to anodic degradation, in simultaneous degradation, the reduction rates for TCA and total organic carbon (TOC) increased from 65.32% and 62.03% to 91.82% and 73.03%, respectively. Meanwhile, the dechlorination rate rose from 64.6 to 80.12%. For simultaneous degradation, the disappearance of TCA, the reduction in the TOC, and the dechlorination of TCA, followed first-order kinetics. The reaction intermediates were detected and, based on the intermediates and the observed kinetics, the effects of the simultaneous degradation of TCA, TOC, and dechlorination of TCA are discussed. The cathode materials, length of the anode dipped into the electrolyte, and Pd loading on the Ni cathode all affected the simultaneous degradation of TCA significantly. The effect of the addition of Fe²⁺ was also investigated. The additive and synergistic effects of the combination of anodic and cathodic degradations on simultaneous degradation are discussed. Based on these results, an analysis of the degradation of TCA suggests that ·OH and ·H/e ^?_aq generated by the action of anodic CGDE, as well as the ·H_ads generated on the Pd-loaded Ni cathode surface, are the key species responsible for the dechlorination of TCA. Furthermore, possible mechanistic routes for the simultaneous degradation of TCA are proposed.

     

Simple Selective Spectrophotometric Method for the Determination of Ruthenium in Carbon Supported Pt-Ru-Ge Catalyst

ABSTRACT

A simple spectrophotometric method for the determination of ruthenium in the presence of platinum in Pt-Ru-Ge catalyst applied in fuel cells has been developed. Platinum catalyst (20% Pt) with carbon support containing 0.5% Ru and 5% Ge was digested in the mixture of HCl+HNO₃ (6+1). Carbon was separated from the examined sample by filtration after dissolution of the metals. Ruthenium was converted into a complex with thiourea (λ_max=640 nm, ε = 2.9·10³ 1 mol^?1 cm^?1) in the medium of 5 M in HCl and 1% in thiourea after 15 min heating at 70 °C. Platinum does not interfere with the determination of ruthenium. Germanium is converted into volatile GeCl₄ and escapes from the examined sample during the digestion step. The content of ruthenium determined in the examined samples of catalyst amounted to 0.49% (RSD = 0.14%).     

Assessment of mobility of heavy metals in two soil types by use of column leaching experiments and chemometric evaluation of elution curves

The objectives of this study were to evaluate the mobility of heavy metals (HMs) in two types of soils (acidic forest soil and neutral agricultural soil) by leaching with calcium chloride solution in column experiments. The screening properties of neutral agricultural soil towards pollution by heavy metals (Ni, Cu, Zn and Cd) are approximately 10 times higher than those of acid forest soil. The neutral agricultural soil, polluted artificially by one pore volume (PV) of an HMs solution of concentration 200 mg L^?1, can screen the leaching of these metals over several hundreds of years. The higher apparent desorption rate and per cent desorption of HMs (especially Cd) in acid forest soil indicated a higher potential of intensive migration of the metals across the profile and indicated potential risk of Cd pollution for this type of soil. The latest approach of artificial neural networks to describe transport of HMs in soil has been also evaluated. Using a simple three-layer perceptron topology with three hidden neurons, the experimental data could be simulated. The results suggested that the pH of soil is a major factor controlling the retention of the heavy metals in the soils.     

Trace metal analyses in honey samples from selected countries. A potential use in bio-monitoring

Honey is a sweet product made by bees using nectar from flowers. Concentrations of Ca, K, Mg, Fe, Zn, Mn, Cu, Pb and Cd were determined in 13 honey samples from the selected regions around the world. Levels of Ca, Mg, Cu, Fe, Zn and Mn were measured using flame atomic absorption spectrometry (FAAS). Potassium concentration was determined via flame photometry. Concentrations of Cd and Pb were determined using the electrothermal technique (ETAAS). It was estimated that the examined samples of honey from Greece, Turkey, Spain, Poland, Mexico, Argentina and Italy were of good quality in terms of metal concentrations (compliant with the norms referring to food products – WHO, Fifty-third Report of the joint FAO/WHO Expert Committee on Food Additives; Technical Report Series 776, Geneva), although the analysed samples were not free of heavy metals. The concentrations of the elements in the honey samples ranged from 2.38 to 9.31 μg · g^?1 for Zn, from 3.86 to 35.10 μg · g^?1 for Fe, from 0.19 to 21.64 μg · g^?1 for Mn, from 49.53 to 1006.90 μg · g^?1 for Ca, from 388.25 to 4761.50 μg · g^?1 for K and from 0.20 to 1.53 μg · g^?1 for Cu and regarding heavy metals from 0.11 to 2.78 μg · g^?1 for Pb and from 0.02 to 0.44 μg · g^?1 for Cd. According to these results it was found that the concentrations of heavy metals in the honey samples (except for alfalfa honey and eucalyptus honey from Italy) were under the acceptable limits for foods set out by the FAO/WHO. It was confirmed that the application of chemometric tools supports the extraction of significant information from analytical data, even though the availability of samples is not fully sufficient (this problem is often encountered in environmental analyses).     

金属离子对氯过氧化物酶在25℃到55℃激活作用以及机理的研究

基于氯过氧化物酶（CPO）的卤化活性分析,发现某些碱土金属（Ca2+, Mg2+）和过渡金属（Co2+, Ni2+）对CPO具有明显的激活及稳定化作用。例如25 ºC时与CPO在纯缓冲溶液中相比,在75 μmol·L-1 Ca2+,90 μmol·L-1 Mg2+,90 μmol·L-1 Ni2+及105 μmol·L-1 Co2+存在时CPO可分别获得1.33,1.37,1.34 及1.27倍的最大相对活性。而在55 ºC,没有金属离子存在时,CPO 30分钟后仅能保留40%的活性,但在Ca2+,Mg2+离子的介质中,CPO的活性可分别保留81% 和 75%。推测这是由于金属离子结合在CPO活性中心周围的酸-碱催化位点Glu183, His105 and Asp106上,通过底物浓集和诱导有利构象来激活CPO. 同时动力学研究表明金属离子对CPO的激活归因于催化效率（kcat）的提高,以及CPO对底物亲和性及选择性的改善。     

Food engineering residues: amino acid composition of hydrolysates and application for the decontamination of metal polluted soils

Several residues of the brewing industry and slaughtering offals were investigated in order to evaluate their potential as raw materials for the hydrolytic preparation of amino acid containing solutions, applicable as extractants in amelioration processes for metal polluted soils. The residues were hydrolysed with 6 mol/L hydrochloric acid and the hydrolysates were analysed for their total nitrogen, TOC, amino acid and heavy metal contents. Then, the leaching capacities of the hydrolysates were examined in a series of batch tests with a contaminated soil.High amino acid yields in relation to the weight of the air-dried raw materials were achieved with blood meal (72.5%) and poultry feather meal (56.6%). The portion of the detected amino acids of the total organic carbon content of the hydrolysates ranged from 38.9% (brewer's spent grain) to 93.6% (blood meal). In extraction tests with hydrolysates adjusted to a total amino acid concentration of 60 mmol/L and to a pH value of 7.0, maximum extraction yields of 50.3% for copper (soil content 279 mg kg^–1) and 38.7% for nickel (soil content 54 mg kg^–1) were reached. An increase of the hydrolysate concentration and of the pH of an amino acid mixture resulted in higher solubilisation of the metals.Dedicated to Prof. Dr. Dieter Klockow on the occasion of his 60th birthday     

129I levels in soils from Ukraine and Slovenia in the last decade

¹²⁹I is important as an environmental tracer of the biogeochemical cycling of iodine and of the dissemination of nuclear pollution, because anthropogenic ¹²⁹I has been released from only few point sources and with its short mixing time its distribution therefore reveals the movement of ¹²⁹I in the environment. A radiochemical neutron activation analysis method was developed to measure the concentration of ¹²⁹I in soil samples. A procedure to pre-concentrate iodine from up to 150?g of soil was developed and validated using IAEA standard reference material IAEA-375 (Chernobyl soil). The method was applied to determine ¹²⁹I/¹²⁷I isotopic ratios as well as ¹²⁹I and ¹²⁷I concentrations in soils from several locations in Ukraine collected in 2006, 1996, 1993 and 1989, and from Slovenia, collected at various places in 2009 and 2006. The ¹²⁷I concentrations in surface soils from Ukraine were in the range 2.3–23.1?µg?g^?1 and for ¹²⁹I (11.1–245.7)?·?10^?8?µg?g^?1 dry matter with the highest value of 1.47?·?10^?3?µg?g^?1 found in a soil sample collected in Yaniv, Ukraine in July 1993. In soil samples from Slovenia ¹²⁷I concentrations ranged 0.73–130?µg?g^?1 and ¹²⁹I (8.0–245.7)?·?10^?8?µg?g^?1. The ¹²⁹I/¹²⁷I isotopic ratios of surface soils from Ukraine were in the range of the order of 10^?9–10^?5 and of 10^?10–10^?8 for soils from Slovenia. The highest isotopic ratio 13.6?·?10^?5 was found in a soil sample collected in Yaniv, Ukraine in July 1993.     

Hydrogen and Methane Production, Energy Recovery, and Organic Matter Removal from Effluents in a Two-Stage Fermentative Process

This study evaluates the potential for using different effluents for simultaneous H₂ and CH₄ production in a two-stage batch fermentation process with mixed microflora. An appreciable amount of H₂ was produced from parboiled rice wastewater (23.9?mL g^?1 chemical oxygen demand [COD]) and vinasse (20.8?mL g^?1 COD), while other effluents supported CH₄ generation. The amount of CH₄ produced was minimum for sewage (46.3?mL g^?1 COD), followed by parboiled rice wastewater (115.5?mL g^?1 COD) and glycerol (180.1?mL g^?1 COD). The maximum amount of CH₄ was observed for vinasse (255.4?mL g^?1 COD). The total energy recovery from vinasse (10.4?kJ g^?1 COD) corresponded to the maximum COD reduction (74.7?%), followed by glycerol (70.38?%, 7.20?kJ g^?1 COD), parboiled rice wastewater (63.91?%, 4.92?kJ g^?1 COD), and sewage (51.11?%, 1.85?kJ g^?1 COD). The relatively high performance of vinasse in such comparisons could be attributed to the elevated concentrations of macronutrients contained in raw vinasse. The observations are based on kinetic parameters of H₂ and CH₄ production and global energy recovery of the process. These observations collectively suggest that organic-rich effluents can be deployed for energy recovery with sequential generation of H₂ and CH₄.     

Simultaneous Determination of Perphenazine and Amitriptyline by Derivative Spectrophotometry

Abstract

Two methods have been developed for the simultaneous determination of Amitryptiline and Perphenazine: the zero-crossing (I) and the derivative ratio spectrum (II) methods and both use the derivative spectrophotometry.

The methods have been applicable in the ranges of 1 to 30 μg·ml^?1 of Amitryptiline (I and II) and between 1 and 8 μg·ml^?1 and from 1 to 7 μg·ml^?1 of Perphenazine for the methods I and II respectively. The accuracy of the proposed methods have been studied and they have been used in the determination of Amitryptiline and Perphenazine in commercially available pharmaceuticals.     

Simple and efficient treatment of high-strength industrial waste water using commercial zero-valent iron

The zero-valent iron (ZVI)/H₂O₂ Fenton system can be considered as an effective solution for the removal of many of the organic pollutants present in the waste waters generated by the drug manufacturing industry. The hydrogen peroxide concentration and dosage rate were studied in order to improve the efficiency of the oxidant in the TOC reduction and, thereby enhance the overall catalytic performance of the ZVI/H₂O₂ Fenton system. TOC reductions of up to 80 % and BOD₅/COD ratios of up to 0.6 were achieved in the waste water as received without dilution (TOC_O approximately 5 g L^?1) using hydrogen peroxide dose-staggering. This showed that the ZVI/H₂O₂ process led not only to a decrease in TOC removal but also to an increase in the biodegradability of the by-products formed. The hydrogen peroxide was consumed more efficiently and very low concentrations of iron dissolved (7 mg L^?1) were obtained in the final effluents. The final values of COD, BOD₅, the suspended solids’ content and the conductivity of the treated waste water met the limits of the Spanish legal industrial discharge, Decree 57/2005 (Ministry of Environment, Local Government and Planning, Community of Madrid, 2005). In addition, the composite thus formed, consisting of zero-valent iron and iron oxide-oxyhydroxides, can be readily removed from the treated effluent, avoiding any post-treatment step.     

Chemical composition and antibacterial activity of Tussilago farfara (L.) essential oil from Quebec,Canada

Abstract

The chemical composition of Tussilago farfara L. essential oil from the Saguenay-Lac-St-Jean region of Quebec, Canada was analyzed by gas chromatography–flame ionisation detector (GC-FID) and gas chromatography–mass spectrometry (GC-MS), and the antibacterial activity of the oil was tested against Escherichia coli and Staphylococcus aureus. Forty-five (45) compounds were identified from the GC profile. The main components were 1-nonene (40.1%), α-phellandrene (26.0%) and ρ-cymene (6.6%). The essential oil demonstrated antibacterial activity against E. coli (MIC₅₀ = 468 µg·mL^?1; MIC₉₀ = 6869 µg·mL^?1) and S. aureus (MIC₅₀ = 368 µg·mL^?1; MIC₉₀ = 773 µg·mL^?1). Dodecanoic acid was found to be active against both bacteria having a MIC₅₀ and MIC₉₀ of 16.4 µg·mL^?1 and 95 µg·mL^?1, respectively for E. coli and a MIC₅₀ and MIC₉₀ of 9.8 µg·mL^?1 and 27.3 µg·mL^?1, respectively for S. aureus. In addition, 1-decene and (E)-cyclodecene were also found to be active against E. coli.     

A Simple and Sensitive Method for the Detection of Trace Pb(II) and Cd(II) based on Nafion‐coated Antimony Film Electrode

Nafion‐coated antimony film electrode (NCAFE) was prepared in situ by simultaneously plated antimony with analytes, and applied to the determination of trace Pb(II) and Cd(II) in non‐deaerated solutions by differential pulse anodic stripping voltammetry (DPASV). Various experimental parameters, which influenced the response of the NCAFE to those metals, were thoroughly optimized and discussed. The results indicated that the sensitivity and resistance to surfactants at the NCAFE were remarkably improved with relative to the antimony film electrode (AFE). In the presence of 5 mg·L^?1 gelatin, the peak heights at the NCAFE showed 4‐fold enhancement for Pb and a 9‐fold enhancement for Cd over a bare AFE. Reproducibility of the sensor was satisfactory, and the relative standard deviations were 4.8% for 20 μg·L^?1 Pb and 3.2% for 25 μg·L^?1 Cd (n=15) with preconcentration time of 180 s. The determination limits (S/N=3) of this sensor were determined to be 0.15 μg·L^?1 for Pb and 0.30 μg·L^?1 for Cd with accumulation time of 300 s. The NCAFE was successfully applied to determining Pb(II) and Cd(II) in vegetable and water samples with satisfactory results.     

Multielement Analysis of South Serbian Strawberry Cultivars by Inductively Coupled Plasma—Optical Emission Spectrometry

The contents of 17 elements in thirteen strawberry cultivars grown in the five districts of Southern Serbia were determined using inductively coupled plasma optical emission spectrometry (ICP-OES). The most abundant elements are K (875–1148 mg?·?kg^?1 fresh weight), P (307–664 mg?·?kg^?1 fresh weight), Ca (192–256 mg?·?kg^?1 fresh weight), and Mg (111–189 mg?·?kg^?1 fresh weight) in all samples. Strawberries were also found to be a good source of Sr (8.05–18.6 mg?·?kg^?1 fresh weight) and Fe (3.09–10.4 mg?·?kg^?1 fresh weight). The contents of As and Cd were below the detection limit (0.0828 mg?·?kg^?1 and 0.0205 mg?·?kg^?1, respectively) in all strawberry samples, while the contents of Ni, Cr, and Cu were below the recommended tolerable levels proposed by Joint Food and Agriculture Organization of the United Nations and World Health Organization Expert Committee on Food Additives, and did not a pose a health risk for the consumer. The application of Duncan’s test showed significant differences between contents of analyzed elements in all strawberry cultivars. The highest mean levels of analyzed elements were detected in strawberries grown in the Topli?ki, Jablani?ki, and P?injski districts. The spike recovery test was used to verify the accuracy of the method, and the spike recovery was in the range 93.8–107.8%. The contents of the metals in strawberry samples were also comparable with values previously reported in the literature.     

The loading of polyoxometalates compound on a biomass derived N-doped mesoporous carbon matrix,a composite material for electrical energy storage

Abstract

A polyoxometalate (POM)-based composite material (NiPW₁₂NP/NMC) was synthesized, in which the nanoparticle of a POM compound (NiPW₁₂NP) distributes on orange juice derived nitrogen doped mesoporous carbon matrix (NMC) homogenously. When employed as a cathode material, NiPW₁₂NP/NMC exhibits high specific capacitance, remarkable rate capability and long-term stability. When the current density is 4?A·g^?1, a specific capacitance as high as 547 F·g^?1 is achieved by NiPW₁₂NP/NMC. With NiPW₁₂NP/NMC serving as cathode and MnO₂ acting as anode, a high performance asymmetric supercapacitor is assembled, which possesses a high energy density of 10.88?Wh·kg^?1 at 0.64?kW·kg^?1. It also shows a good rate capability, when the current density increases from 4 to 12?A·g^?1, its specific capacitance decreases from 113 to 88 F·g^?1, with 77.9% capacitance retention. After 5000 cycles charge-discharge experiments, 92.8% of its capacitance can be maintained, which exhibits good stability.