Removal and Preconcentration of Cobalt Ions from Aqueous Media Using ImHA Packed Column by On-Line SPE System

This work assesses the use of immobilized humic acid (ImHA) onto aminopropyl silica (APS) as a sorbent for the removal and preconcentration of trace amounts of cobalt ions by on-line solid phase extraction (SPE) technique in the column system prepared in our laboratory. Different parameters, such as the effect of the pH, concentration, and flow rate, were studied and throughput was observed by a UV detector. All SPE steps were monitored by breakthrough curves used to visualize distribution of cobalt concentration between mobile and solid phase. The solutions collected from stripping steps were analyzed in atomic absorption spectrometer (AAS) and the amount of sorbed ions was calculated. Sorption characteristics were evaluated by using common adsorption isotherms and Scatchard plot analysis. From the obtained results, it was seen that sorption mechanism of cobalt ions were fitted to Langmuir model on a large scale and thought to be localized. Mean free energy (E?=?40.82?kJ?mol^?1) calculated from D-R isotherm showed that chemical interactions are more effective than physical interactions. This investigation reveals a new, simple, environmentally friendly, and cost-effective method for removal and preconcentration of cobalt ions from aqueous solutions by a new aminopropyl silica-immobilized humic acid material.     

Magnetic Solid-Phase Extraction Based on Modified Iron Oxide Nanoparticles for the Preconcentration of Ultra-Trace Amounts of Copper Ions in the Environmental and Plant Samples and its Determination Using FAAS

In the present work, magnetic iron oxide nanoparticles (MIONPs) coated with sodium dodecyl sulfate (SDS) and modified with 1-(2-pyridylazo)-2-naphthol (PAN) as a new nanoparticle were prepared and used as an adsorbent for the extraction and preconcentration of copper ions. After adsorption, copper ions were desorbed with nitric acid (HNO₃), followed by determination with flame atomic absorption spectrometry (FAAS). The extraction conditions0. were investigated systematically. The linear range 3.0–500.0 ng mL^?1 and the detection limit of 0.6 ng mL^?1 were obtained. The relative standard deviation (RSD) of the method for seven replicate determinations of 0.1 µg mL^?1 of Cu(II) was 2.2%. The method was applied for the determination of Cu(II) in different water samples with good trueness. The accuracy was also evaluated through analyses of a certified reference material (CRM TMDW-500).     

Preparation of Modified Magnetic Cobalt Nanoparticles as a New Magnetic Sorbent for the Preconcentration and Determination of Trace Amounts of Lead Ions in Environmental Water and Soil (Air-Dust) Samples

In this study, cobalt magnetic nanoparticles (MNPs) were synthesized and then modified by sodium dodecyl sulfate (SDS) and 2-(5-bromo-2-pyridylazo)-5-diethyl aminophenol ligand (5-Br-PADAP), through a chemical precipitation method. Characterization of the prepared MNP adsorbents was performed by Fourier transform infrared and transmission electron microscopy. Cobalt nanoparticles (NPs) surface modified with SDS and 5-Br-PADAP was evaluated as a nanoparticulate solid-phase extraction (SPE) absorbent for lead ions Pb(II) from water and standard samples, prior to its flame atomic absorption spectrometry determination. Effects of pH, amount of sorbent, desorption solvent, adsorption time, desorption time, and interfering ion concentration on extraction efficiency were investigated. Under optimal conditions, the calibration curve was linear in the range of 1.0–500 ng mL^?1of Pb(II) with R² = 0.998. Detection limit was 1.6 ng mL^?1 in the original solution (3S_b/m), and the relative standard deviation for replicate determination of 0.5 μg mL^?1 Pb(II) was ±2.7%.     

Determination and Speciation of Aluminum in Environmental Samples by Cation Exchange High-Performance Liquid Chromatography with High Resolution ICP-MS Detection

A cation-exchange high-performance liquid chromatography with high resolution inductively coupled plasma mass spectrometric detection (CE-HPLC/ICP-MS) was developed for the determination and the speciation of aluminum in environmental samples. Three types of aluminum species (AlL_x ^<+2, AlL_x ²⁺, Al³⁺) were separated from one another, and were determined with the present system. The comparison of the present system with an established CE-HPLC with fluorimetric detection using 5-sulfo-8-quinolinol (CE-HPLC/FL) was described. The present system showed better sensitivity for aluminum than CE-HPLC/FL. Moreover, the analytical results for soil extract and lake water samples obtained with both methods were in good agreement with each other.     

Determination of Environmental Quality of a Drinking Water Reservoir by Remote Sensing, GIS and Regression Analysis

Istanbul, housing a population over ten million and with population increase rate of approximately twice that of Turkey, is one of the greatest metropolitan cities of the world. As a consequence of rapid population growth and industrial development, Omerli watershed is highly affected by wastewater discharges from the residential areas and industrial plants. The main objective of this study is to investigate the temporal assessment of the land-use/cover of the Omerli Watershed and the water quality changes in the Reservoir. The study is mainly focused on the acquisition and analysis of the Satellite Probatoire de l'Observation de la Terre (SPOT) (1993), Indian Remote Sensing satellite (IRS) (1996 and 2000) and Landsat Thematic Mapper (TM) (2004, 2005, and 2006) satellite images that reflect the drastic land-use/cover changes utilizing the ground truth measurements. The rapid, uncontrolled, and illegal urbanization coupled with insufficient infrastructure has caused the deterioration of the water quality within the past two decades in the Omerli watershed. The water quality analysis of the drinking water Reservoir within the watershed is investigated using 2006 dated Landsat TM satellite digital data. The results are compiled and compared with the water quality measurements of parameters like total nitrogen (TN), the total phosphorus (TP), chlorophyll a (CL) and total dissolved solids (TDS). The observed reflectance shows a strong relationship with the water quality parameters and thus, the satellite data proved to provide a useful index of TN, TP, CL and TDS. Moreover, the linkage between the water quality parameters and the individual band reflectance values are supported by multiple regression analysis.     

Simultaneous Determination of Phorate and Oxyfluorfen in Well Water Samples with High Accuracy by GC-MS After Binary Dispersive Liquid-Liquid Microextraction

The potential risk of pesticides to cause harm to humans and other organisms even at trace levels calls for sensitive and accurate analytical techniques for their simultaneous qualitative and quantitative determinations. In this study, a sensitive binary dispersive liquid-liquid microextraction (B-DLLME) strategy was developed for the simultaneous determination of phorate and oxyfluorfen by gas chromatography mass spectrometry after extraction/preconcentration from aqueous solution. An experimental design was used to optimize parameters of the B-DLLME method to obtain maximum outcome. Under the optimum conditions of B-DLLME, the limit of detection (LOD) for phorate and oxyfluorfen were found to be 0.41 μg L^?1 and 0.54 μg L^?1, respectively. The detection limits correlate to about 37 and 73 folds enhancement in detection powers when compared to direct GC-MS determination of phorate and oxyfluorfen, respectively. In order to find out the applicability of developed method to real samples, recovery tests were performed for 20 μg L^?1 of phorate and oxyfluorfen spiked in well water samples. Percent recovery values were found to be 94.5% for phorate and 101.9% for oxyfluorfen.     

Determination of trifloxystrobin and its metabolites in Hawaii soils by ASE-LC-MS/MS

Analytical methods for the determination of trifloxystrobin and four of its metabolites were developed in a leaching study conducted in Hawaii. To duplicate plots at each of five locations representing various agricultural areas in Hawaii, trifloxystrobin was applied at label rates and allowed to leach under normal rain and irrigation conditions. Soil samples were collected at weekly to monthly intervals and the residual concentrations of trifloxystrobin and metabolites measured. A quantitative analytical method for their determination in various soil samples was developed using accelerated solvent extraction (ASE), coupled with liquid chromatography-tandem mass spectrometry. Extraction solvent with various ratios of methanol to water, addition of EDTANa2 to the extract solvent, and ASE cell temperature were adjusted to improve recovery. Deuterated (E, E)-trifloxystrobin was chosen as the internal standard of the analytical method. The limit of quantitation was 2.5 ppb in the soil for trifloxystrobin and its metabolites. Laboratory aerobic degradation studies with the soils from the five sites were also conducted to measure the same compounds.     

Separation of Ag(I) Ions from Lepidium draba L. Plant and Water and Standard Samples by Carrier Element-Free Coprecipitation Method Prior to their Flame Atomic Absorption Spectrometric Determination

In this work, silver iodide (Ag(I)) ions were separated via the carrier element-free coprecipitation (CEFC) method using an organic coprecipitating agent, 1,6-diamino-4-(4-chlornphenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile [DCODD] prior to its determination by ?ame atomic absorption spectrometry (FAAS). Analytical parameters including pH of aqueous solution, amount of DCODD, standing time, centrifugation rate and time, and sample volume were studied and optimized. Under the best experimental conditions, it was found that extraction can be performed from the sample volume of 500.0 for silver ion (preconcentration factor of 100.0). Linearity was maintained between 0.006 and 1.50 µg.mL^?1 for silver. Detection limit for silver based on 3Sb was 1.60 ng.mL^?1. The relative standard deviation of eight replicate measurements of 0.20 µg.mL^?1of silver was 2.10%. Finally, the developed method was successfully applied to extraction and determination of the silver ions in the Lepidium draba L plant, water and standard samples and satisfactory results were obtained.     

秸秆碳和硫酸铝对富营养化水体中氮磷的吸收去除效应及其影响因素

为解决中国水体富营养化问题,将秸秆碳与硫酸铝作为一种有效吸附水体中总氮、总磷的吸附剂,通过室内模拟试验,采用平衡吸附法,考察了秸秆碳和硫酸铝投加量、pH值、振荡时间、温度、扰动、秸秆碳粒径等不同环境因素条件下对吸附效果的影响。结果表明:在秸秆碳和硫酸铝投加量为0.2 mg/L、振荡时间为120 min的条件下,吸附效果最好,去除率可达80%以上。通过对各因素与秸秆碳、硫酸铝对总氮和总磷的吸附效果分析得知,加入适量的秸秆碳和硫酸铝,可以降低水体中总氮、总磷的含量,吸附效果对温度、振荡时间、pH值变化敏感,这也为解决水体富营养化问题提供了基础依据。     

Evaluation of Phenol/Aniline (Single and Binary) Removal from Aqueous Solutions onto Hyper-cross-linked Polymeric Resin (Macronet MN200) and Granular Activated Carbon in Fixed-Bed Column

This work was conducted to evaluate the sorption performance of hyper-cross-linked Macronet resin (MN200) compared to the granular activated carbon in order to remove phenol and aniline from aqueous solution in both single and binary solutions. Fixed-bed column experiments were used to obtain the breakthrough curves. The experimental data were fitted to the Thomas, Bed Depth Service Time and Yoon?CNelson models, well-established fixed-bed sorption models. The theoretical sorption capacities obtained by the Thomas model were in good agreement to the breakthrough capacities determined from the sorption data. The sorption capacity decreased in binary sorption for resin MN200, while activated carbon reported similar (aniline) or higher (phenol) sorption performance indicating a synergistic effect between both solutes on the activated carbon surface. A good prediction of the breakthrough curves in binary solution was obtained by using an approach that considers a simple model to describe a breakthrough curve (Thomas) and modified isotherm equilibrium. The resin MN200 fixed-bed columns were easily regenerated by using a methanol solution, reporting more above of 90% of recovery for both solutes, while about 50% was the recovery of activated carbon after single experiments. The regeneration after the binary sorption experiments reported a decrease in the solute recovery, effect that was especially evident for activated carbon.     

Determination of Cadmium in Tap,Sea and Waste Water Samples by Vortex-Assisted Dispersive Liquid-Liquid-Solidified Floating Organic Drop Microextraction and Slotted Quartz Tube FAAS After Complexation with a Imidazole Based Ligand

This study presents a combination of dispersive liquid-liquid-solidified floating organic drop microextraction (DLLSFODM) and slotted quartz tube (SQT) with conventional flame atomic absorption spectrometry (FAAS) to improve the sensitivity for cadmium determination. A ligand namely 2-(4-methylphenyl)-1H-imidazo-[4,5-f]-[1,10]-phenanthroline which has not been used in trace analyte determination was used to form a cadmium complex. Stepwise optimization of parameters affecting complex formation (pH, ligand, and buffer solution) and extraction (extraction and dispersive solvents, salt effect and mixing) was done to maximize cadmium absorbance. The slotted quartz tube was fitted onto the flame burner and optimized to increase residence time of atoms in the flame. Instrumental parameters such as sample and fuel flow rate were also optimized to further enhance the absorbance signal for cadmium. Using optimal parameters and values, the limits of detection and quantification were determined to be 0.81 and 2.69 μg L^?1, respectively. Low percent relative standard deviations (<?6.0%) indicated good precision for both extraction and instrumental measurements. Recovery tests were used to determine the accuracy of the method and the recovery results obtained were between 88 and 113%.

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Graphical Abstract ?

     

杜马斯-碳氮分析仪法测定缓控释氮肥释放氮量

为了提高缓控释氮肥释放氮量的测定效率,避免样品消煮过程中的强酸与毒害气体物质等问题,该研究基于杜马斯法原理,利用碳氮分析仪,测定2种缓控释氮肥在25℃静水释放试验中,第1、3、7、14和28天肥料浸出液的氮浓度,计算缓控释氮肥释放氮量,并与传统常规的凯氏蒸馏滴定法测定结果间进行比较。结果表明：2种方法肥料浸出液中N浓度测定结果之间呈极显著线性相关关系,相关系数r=0.991（n=30,P<0.01）。依据2种方法测定结果计算的氮素养分释放期彼此相差小于20%,符合国家标准《GB/T 23348-2009缓释肥料》及化工行业标准《HG/T 4215-2011控释肥料》的允许差范围。相比较传统的凯氏蒸馏滴定法,杜马斯-碳氮分析仪法测定缓控释氮肥释放氮量过程简便快捷,样品无需消煮,不涉及强酸不产生有毒有害物质。该结果为缓控释氮肥释放氮量新的测定方法提供了科学依据。     

Removal of Remazol Brilliant Blue Dye from Dye-Contaminated Water by Adsorption Using Red Mud: Equilibrium, Kinetic, and Thermodynamic Studies

Utilization of industrial solid wastes for the treatment of wastewater from another industry could help environmental pollution abatement, in solving both solid waste disposal as well as liquid waste problems. Red mud (RM) is a waste product in the production of alumina and it poses serious pollution hazard. The present paper focuses on the possibility of utilization of RM as an adsorbent for removal of Remazol Brilliant Blue dye (RBB), a reactive dye from dye-contaminated water. Adsorption of RBB, from dye-contaminated water was studied by adsorption on powdered sulfuric acid-treated RM. The effect of initial dye concentration, contact time, initial pH, and adsorbent dosage were studied. Langmuir isotherm model has been found to represent the equilibrium data for RBB?CRM adsorption system better than Freundlich model. The adsorption capacity of RM was found to be 27.8?mg dye/g of adsorbent at 40?°C. Thermodynamic analysis showed that adsorption of RBB on acid-treated RM is an endothermic reaction with ?H ⁰ of 28.38?kJ/mol. The adsorption kinetics is represented by second-order kinetic model and the kinetic constant was estimated to be 0.0105?±?0.005?g/mg?min. Validity of intra-particle diffusion kinetic model suggested that among the mass transfer processes during the dye adsorption process, pore diffusion is the controlling step and not the film diffusion. The process can serve dual purposes of utilization of an industrial solid waste and the treatment of liquid waste.     

Extraction of azadirachtin A from neem seed kernels by supercritical fluid and its evaluation by HPLC and LC/MS

A new supercritical extraction methodology was applied to extract azadirachtin A (AZA-A) from neem seed kernels. Supercritical and liquid carbon dioxide (CO(2)) were used as extractive agents in a three-separation-stage supercritical pilot plant. Subcritical conditions were tested too. Comparisons were carried out by calculating the efficiency of the pilot plant with respect to the milligrams per kilogram of seeds (ms/mo) of AZA-A extracted. The most convenient extraction was gained using an ms/mo ratio of 119 rather than 64. For supercritical extraction, a separation of cuticular waxes from oil was set up in the pilot plant. HPLC and electrospray mass spectroscopy were used to monitor the yield of AZA-A extraction.     

Determination of Thallium and Other Elements (As,Cd, Cu,Mn, Pb,Se, Sb,and Zn) in Water and Sediment Samples from the Vicinity of the Zinc-Lead Smelter in Poland (3 pp)

Background, Goal and Scope   The aim of this study was to check the concentration of some elements in water samples collected near Pb-Zn mining and smelting works and comparison of the obtained data with results achieved for sediment samples originated from the same reservoirs. Objective   Here, 8 water samples and 3 bottom sediments collected from water reservoirs in the vicinity of 3 big Polish Pb-Zn smelters were analysed.Methods   Water analysis was performed after filtration through a 0.45 &#181;m filter and pH adjustment to 2. For decomposition of dried sediment samples, microwave assisted digestion with total dissolution of silicate matrix was applied. The elements studied were determined using ICP-MS and ICP-OES methods. Results and Discussion   The concentrations of most studied elements in water samples were on the 0.X &#181;g/L level, while only the contents of Tl, As, Mn, Cd, Pb and Sb in two water reservoirs were above the limits established for drinking water. The content of studied metals in sediments was in a wide range from X mg/kg (Se and Sb) to X000 mg/kg (Pb and Zn).Conclusions  and Recommendation. The study indicates that the impact of Tl, As, Cd, Cu, Mn, Pb, Zn, Se and Sb on bottom sediments is much more extensive than on the water in ponds located in the vicinity of a post-flotation waste heap. Monitoring of surface and underground waters, if limited only to the dissolved elements, can lead to faulty conclusions about environmental pollution. The bottom sediments mainly contain easily mobilised phases, and water-sediment equilibrium could be changed easily.     

Determination of coumaphos and its oxygen analog in eggs and milk by using a multiresidue method with liquid chromatographic quantitation and capillary gas chromatographic/mass spectrometric confirmation

A multiresidue method for carbamate insecticides was adapted for the determination of coumaphos and its oxygen analog in eggs and milk. Eggs were extracted with acetonitrile and milk was extracted with acetone. Co-extractives were removed using liquid partitioning and charcoal column procedures described in the carbamate method. Coumaphos and its oxygen analog were determined by using a high performance liquid chromatograph equipped with a fluorescence detector. Recovery studies were performed for the 2 compounds at levels of 0.01 and 0.10 ppm in eggs and 0.01 and 0.02 ppm in milk. Overall average recovery was 100% (range 95-109%). In a trial of the method by another laboratory, the recovery of coumaphos and its oxygen analog from milk averaged 87 and 96%, respectively. Data are presented on the capillary gas chromatographic/mass spectrometric confirmation of coumaphos residues.     

Determination of 28 Elements in Aquatic Moss Fontinalis Antipyretica Hedw. and Water from the Upper Reaches of the River Nysa (CZ,D), by ICP-MS,ICP-OES and AAS

The concentrations of 28 elements in samples of the bryophyte F. antipyretica Hedw collected from various sites on the upper reaches of the River Nysa and its main tributaries were determined. These results were compared with similar analyses of water samples collected at the same sites. So, it was possible to determine the elemental composition of the water both directly and indirectly, using a bioindicator organism. Analyses were carried out using different instrumental techniques (ICP-MS, ICP-OES, AAS), some elements being analysed by both ICP-MS and ICP-OES. Functional regression analysis showed that for some of these elements, namely Al, Ba, Fe, Sr and Ti in moss, and Ba, Ca and Zn in water samples, there was no significant difference (p < 0.05) in the concentrations determined by both techniques. The coefficients of correlation moss/water for each element were calculated, but they were in general low. However the coefficients of correlation between different elements were in general good. Finally, the elemental concentrations in the aquatic moss were also used to assess the level of contamination in the area of study, through the calculation of CF (Contamination Factor) values.     

Determination of the 2H/1H and 15N/14N ratios of Alkylpyrazines from coffee beans (Coffea arabica L. and Coffea canephoravar. robusta) by isotope ratio mass spectrometry

The delta15N(AIR) and delta2H(VSMOW) data for several alkylpyrazines formed during the roasting process of coffee are reported. Samples of commercially available roasted (n = 9) as well as self-roasted (n = 8) coffee beans (Coffea arabica L. and Coffea canephora var. robusta) of different origins were investigated. By use of extracts prepared by simultaneous distillation extraction (SDE) and subsequently fractionated by liquid chromatography on silica gel, on-line capillary gas chromatography-isotope ratio mass spectrometry was employed in the combustion (C) and pyrolysis (P) modes (HRGC-C/P-IRMS) to determine the delta15N(AIR) and delta2H(VSMOW) values, respectively. In addition to the constituents of coffee beans, data for commercial synthetic alkylpyrazines and substances declared to be "natural" were determined. The delta15N(AIR) data for coffee alkylpyrazines under study-2-ethyl-5-methylpyrazine (1) and 2-ethyl-6-methylpyrazine (2) (measured as sum 1/2), 2-ethyl-3-methylpyrazine (3), 2-methylpyrazine (4), 2,5-dimethylpyrazine (5) and 2,6-dimethylpyrazine (6) (measured as sum 5/6), and 2,3-dimethylpyrazine (7), as well as 2,3,5-trimethylpyrazine (8)-varied in the range from +8.3 to -10.2 per thousand, thus revealing their biogeneration from amino acids (delta15N(AIR) ranging from +8 per thousand to -10 per thousand). The delta2H(VSMOW) values were determined in the range from -5 per thousand to -127 per thousand. Owing to the analytical differentiation observed between coffee alkylpyrazines and synthetic/"natural" samples of 3, 4, and 7, authenticity assessment of coffee-flavored products seems to be promising, provided that extended data will be available in the future. In the literature, there were no IRMS data available for the alkylpyrazines (1-8) under study.