Synthesis of 2,3-dihydroxynaphthalene-functionalized Amberlite XAD-4 resin: Applications for the separation and preconcentration of trace metal ions prior to their determination by inductively coupled plasma atomic emission spectrometry

A simple, sensitive column solid-phase extraction procedure for separation and preconcentration of Cu(II), Ni(II), Co(II), and Cd(II) in spiked and natural water samples using 2,3-dihydroxynaphthalene-functionalized Amberlite XAD-4 (XAD-4-DHN) chelating resin prior to their determination by inductively coupled plasma atomic emission spectrometry was discussed. The optimum experimental parameters such as pH, volume of sample and eluent, flow-rates of uptake and stripping, and sorption capacity of the chelating resin, were evaluated. The effect of the electrolytes and the cations on the preconcentration of metal ions was also investigated. The chelating resin could be reused for more than 20 cycles of sorption–desorption without any significant change (<1.0%). Recoveries obtained from this method range from 96 to 102% with R.S.D of 2.50 (n = 4). The detection limits for Cu(II), Ni(II), Co(II), and Cd(II) were found to be 1.9, 0.9, 1.2 µg, and 1.4 µg L^?1, respectively. The proposed method was applied for the determination of Cu(II), Ni(II), Co(II), and Cd(II) in spiked, tap water, and river water samples.     

Microbiological and mycotoxicological contamination in Slovenian primary grain production

This study was aimed at investigating the contamination of grains, which are grown and used for animal diets by Slovene farmers. A total of 107 samples were examined for mesofilic aerobic molds and yeasts. The leading contaminants among molds were from Fusarium spp., detected in 73 samples, mostly in maize (50). In accordance with the European Feed Microbiology Organisation criteria, 68% of all tested samples were of the quality level I, with normal microbiological flora, and 9% of samples were estimated as quality level IV and not suitable for animal feed. Using liquid and gas chromatography methods, the presence of various mycotoxins (expressed as 12% of moisture content) was found in 77% of all samples; mostly deoxynivalenol (71%) in concentration of 150–14,420 µg kg^?1, followed by zearalenone (32%, 20–640 µg kg^?1), fumonisin B1 (31%, 10–4863 µg kg^?1), fumonisin B2 (22%, 10–1629 µg kg^?1), while HT-2 and T-2 toxins were found in low concentration in two samples, and aflatoxin B1 and ochratoxin A in one sample. By statistical evaluation, significant positive correlations were noted between the presence of deoxynivalenol and zearalenone as well as between fumonisin B1 and B2.     

Removal of arsenic by Acidothiobacillus ferrooxidans bacteria in bench scale fixed-bed bioreactor system

In the present study arsenic contaminated simulated water and groundwater was treated by the combination of biological oxidation of tri-valent arsenite [As (III)] to penta-valent arsenate [As (V)] in presence of Acidothiobacillus ferrooxidans bacteria and its removal by adsorptive filtration in a bioreactor system. This method includes the immobilisation of A.ferrooxidans on Granulated Activated Carbon (GAC) capable of oxidising ferrous [Fe (II)] to ferric [Fe (III)]. The Fe (III) significantly converts the As (III) to As (V) and ultimately removed greater than 95% by the bed of GAC, limestone, and sand. The significant influence of Fe (II) concentration (0.1–1.5?gL^?1), flowrate (0.06–0.18?Lh^?1), and initial As (III) concentration (100–1000?µgL^?1) on the arsenic removal efficiency was investigated. The simulated water sample containing the different concentration of As (III) and other ions was used in the study. The removal of other co-existing ions present in contaminated water was also investigated in column study. The concentration of arsenic was found to be <10?µgL^?1 which is below Maximum Contaminant Level (MCL) as per WHO in treated water. The results confirmed that the present system including adsorptive-filtration was successfully used for the treatment of contaminated water containing As (III) ions.     

Hair burning and liming in tanneries is a source of pollution by arsenic,lead, zinc,manganese and iron

Heavy metals in the environment may be toxic for human and animals. Tanneries are a source of pollution by heavy metals. There is little information on heavy metals pollution in tanneries, especially on metals produced by the process of hair burning and liming. Liming is the first stage of chemical treatment where animal hair or wool is removed with sodium sulphide and calcium oxide. Here we studied cow, goat, buffalo and sheep hair, conventional liming agents and liming wastewaters from several sources. Samples were acid-digested and aliquots were analysed by atomic absorption spectroscopy following APHA standard method to measure concentrations of arsenic, lead, cadmium, zinc, manganese and iron. Results show that the range of metal contents in hair or wool and liming agents are 1.3–8.2 mg/kg for arsenic, 0.02–21.8 mg/kg for lead, 17.7–121.0 mg/kg for manganese, 7.3–141.1 mg/kg for zinc and 119.6–10613.8 mg/kg for iron. Liming wastewaters contain 1.9–5.6 µg/L arsenic, 0.03–6.05 µg/L lead, 38.6–139.0 µg/L manganese, 144.0–171.5 µg/L zinc and 399.5–1069.0 µg/L iron. Cadmium was below detection limits. This is the first investigation that reveals that hair burning liming operation is a potential source of heavy metals in the environment.     

Effervescence assisted dispersive liquid–liquid microextraction followed by microvolume UV-Vis spectrophotometric determination of surfactants in water

The novel and simple methods for the sensitive determination of cationic and anionic surfactants in water based on effervescence assisted dispersive liquid–liquid microextraction and microvolume UV-Vis spectrophotometry have been developed. The method involves ion-pair extraction of cationic and anionic surfactants with organic dyes (methyl orange and azure A, respectively) during the dispersion of extraction solvent (CHCl₃) by CO₂ bubbles which are formed by the injection of a mixture of the extraction solvent and proton donor solvent into the sample solution which contains carbonate-ions as effervescency agent. The analytical performance of the proposed procedure was compared with the conventional dispersive liquid–liquid microextraction. Appropriate experimental conditions for both methods were investigated. The absorbances of the colored extracts at wavelengths of 440 and 625 nm obey Beer's law within the range of 0.1–5.0 mg/L for both cationic and anionic surfactants. The limit of detection (LOD) obtained using the effervescence assisted extraction method was 30 µg/L for cationic and anionic surfactants. The proposed methods were successfully applied to determination of surfactants in water samples.     

Ecotoxicological assessment of sediment from Texcalac River and agricultural soil of riverside area,in Tlaxcala,Mexico

This study assesses the potential risk of Texcalac River and riparian area. The p,p′ DDT and ∑DDTs levels in agricultural soils (3.9–208.0?µg/kg) and in surface sediments (0.6–137?µg/kg) surpassing the guidelines for protection of aquatic life (75% > TEC). The ∑PCBs concentration oscillated from 135 to 93941?µg/kg; the half of sediments exceeded the international guidelines (PEL, PEC), as well as two soils (SQGE?=?500?µg/kg). The TEQ concentration of four PCB-DL varied between 0.1 and 24.9?µg TEQ/kg, chiefly affected by PCB 169. Five sediments were lethal for E. foetida, two resulted to be cytotoxic and the 58% produced genotoxicity higher than negative control (A?=?0.28?±?0.05; DICA?=?72.5?±?16.9 au). Likewise, 31.6% of samples increased the micronuclei frequency in V. faba in comparison with negative control. The analytical data and the bioassays results suggest a significant and immediate risk to exposed biota of this region, highlighting a specific area in Texcalac River and other one in Sambrano Ravine. It is necessity assess the dispersion of pollutants and perform biomonitoring studies that display the exposure levels in biota with the goal to characterise the ecotoxicological risk.     

Electrochemical hydride generation of tin(II) and its determination by electrothermal atomic absorption spectrometry with in situ trapping in the graphite tube atomizer

An electrolytic hydride generation system for the determination of tin(II) by means of batch electrochemical hydride generation-electrothermal atomic absorption spectrometry (EcHG-ETAAS) with in situ trapping in a graphite tube atomizer is described. The effects of four permanent chemical modifiers – palladium, tungsten, iridium, and platinum – for graphite tube treatment on analyte absorbance and the effects of four cathode materials, i.e., Pb, Sn, Pb–Sn alloy, and glassy carbon, are checked. Three electrolytes, i.e., nitric acid, sulfuric acid, and hydrochloric acid, are examined as catholyte solutions. The influence of several parameters on EcHG is investigated using multivariate and univariate methods. Interferences of some concomitant ions are evaluated. The calibration curve is linear from 1 to 200?µg?L^?1, with a detection limit of 0.8?µg?L^?1 and a relative standard deviation of 6.2% (n?=?3) for 100?µg?L^?1 Sn(II). The proposed method was successfully applied in the analysis of real environmental water samples and reference materials, and good spiked recoveries over the range of 93.1–115% were obtained. The proposed technique provides a means for developing hydride generation of other elements.     

Simultaneous measurements of arsenic and sulfide using diffusive gradients in thin films technique (DGT)

Diffusive gradients in thin films technique (DGT) is a dynamically passive sampling technique which has been applied increasingly to the environmental monitoring field. In the preliminary period, the DGT with zirconium hydroxide-silver iodide as the binding phase (ZrO-AgI DGT) has been developed for the determination of sulfide (S(II)). On this basis, this paper developed its determination method for inorganic arsenite (As(III)) to further realize the simultaneous and high-resolution measurements of labile inorganic As and S(II) in sediments. ZrO-AgI binding gel had a strong ability in adsorbing and fixing As(III), showing a linear increase in the initial 12.5 min. After saturation of S(II) on ZrO-AgI binding gel, the adsorption rate and adsorption capacity of As(III) reduced by 8 and 14%, respectively. A stable elution rate (89.1 ± 2.2%) was obtained by extraction of As(III) on the binding gel using a mixture solution of 1.0 M NaOH and 1.0 M H₂O₂ (1:1). The DGT capacity of As(III) determined by the ZrO-AgI DGT was 23.6 μg cm^?2. DGT uptakes of As(III) were independent of pH (4.0–9.0) and ionic strength (0.01–100 mM), and they did not interfere with each other during the uptake process. Simultaneous measurements of labile As and S(II) in four sediment cores of Taihu Lake (China) with ZrO-AgI DGT showed that they had similarly vertical distributions in the top 16-mm layer in one core and in the whole profile up to the 35 mm depth in two cores. It likely reflected a simultaneous release of As and S(II) in sediments by synchronous reduction of As-hosted oxidized iron and sulfate, respectively. The simultaneous decreases of labile As and S(II) from their co-precipitation (e.g., As₂S₃) were not obvious in deeper sediment layer through the measurement with ZrO-AgI DGT.     

Neurotoxicity and oxidative stress induced by permethrin in gills of the freshwater mussel Unio ravoisieri

Pyrethroids are contaminants found in the aquatic environment, and their toxicological effects on aquatic organisms have received extensive attention. However, the impact on freshwater bivalve of exposure to these chemicals is still largely unknown. Freshwater mussels Unio ravoisieri were exposed to two nominal permethrin (PM) concentrations C1?=?50?µg/L and C2?=?100?µg/L during 7 days. The measured concentrations of PM using gas chromatography (GC/ECD) in the treated aquariums were, respectively, 28.7–62.3?µg/L. Catalase (CAT), Glutathione-S-transferase (GST), and Acetylcholinesterase (AChE) activities, Glutatione (GSH) and Malondialdehyde (MDA) levels were determined in gills of U. ravoisieri. Significant increase in CAT activity by the lowest concentration and decrease by highest concentration were observed. Additionally, GST activity was increased in a concentration-dependent manner. However, statistically significant decrease in GSH levels (about 39%) was observed only at high concentration of this compound (100?µg/L). PM generated an increase in MDA levels reaching the highest value at the high concentration. AChE activity of mussel ranging from 51% inhibition at lowest concentration 50?µg/L to 89% inhibition at highest concentration 100?µg/L. The results indicated that oxidative stress and cell damage might be one of the main mechanisms of PM toxicity to freshwater mussels.     

Abstracts to forthcoming papers

Food is the major source of metal exposure for the nonsmoking general population. Food samples of plant and animal origin from Ismailia, Egypt, were analyzed for the content of cadmium (Cd), lead (Pb), chromium (Cr), zinc (Zn), and copper (Cu) using AAS. The Cr, Zn, and Cu concentrations were in the range of 1.7–249?µg?kg^?1 wet weight (ww), 2–66?mg?kg^?1?ww, and 0.5–3.46?mg?kg^?1?ww, respectively. The mean daily intake of Cr, Zn, and Cu was 28.9?µg day^?1, 8.55?mg day^?1, and 1.7?mg day^?1, respectively. The intake estimates are within the range of the recommended intake established internationally. Concentrations of Cd and Pb were in the range of 10–321?µg?kg^?1?ww and 31–1200?µg?kg^?1?ww, respectively. The weekly dietary intake for Cd and Pb (4.02 and 20.4?µg?kg^?1 b.w, respectively) is lower than the FAO/WHO PTWI. Bread is the foodstuff that provided the highest rate of Pb and Cd (62 and 46% of the daily intake) to adults in Ismailia city.     

The accumulation levels of heavy metals (Ni,Cr, Sr, & Ag) in marine algae from southwest coast of India

In the context of use of marine algae as biological indicators of heavy metal pollution in coastal waters, six species of marine algae collected from the southwest coast of India were analysed for the levels of heavy metals (Ni, Cr, Sr, and Ag). Interspecies and interclass variations were determined on a spatial and temporal scale. The metal contents varied in the ranges, Ni: 0.20–21.06?µg?g^?1 (mean?=?10.13?µg?g^?1), Cr: non-detectable level (ND)–37.18?µg?g^?1 (mean?=?13.86?µg?g^?1), Sr: 2.19–103.90?µg?g^?1 (mean =?29.40?µg?g^?1), and Ag: ND–6.39?µg?g^?1 (mean?=?1.80?µg?g^?1). Ni and Cr contents were of similar magnitude to those reported for algae from polluted areas.     

Genotoxic and cytotoxic in vitro evaluation of ivermectin and its formulation ivomec® on Aedes albopictus larvae (CCL-126™) cells

Genotoxic effects of ivermectin (IVM) and its commercial formulation ivomec® (IVM 1.0%) were studied on Aedes albopictus larvae (CCL-126?) cells by sister chromatid exchange (SCE) and single cell gel electrophoresis (SCGE) while cytotoxicity was determined by cell-cycle progression (CCP), proliferative rate index (PRI), mitotic index (MI), 3(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT), and neutral red (NR) endpoints within a 1–250 µg mL^?1 concentration range. While IVM and ivomec® did not markedly affect SCE frequencies, these agents induced DNA-strand breaks enhancing both slightly damaged and damaged cells at 25–50 and 5–50 µg mL^?1 IVM and ivomec®, respectively. Both compounds exerted a delay in CCP and reduction of PRI at 10 µg mL^?1. Cytotoxicity was observed at concentrations higher than 25 µg mL^?1. A marked reduction of about 98% and 94% of MI compared to controls was noted with 25 µg mL^?1 of IVM and ivomec®, respectively. NR and MTT assays revealed that both compounds induced a cell growth inhibition within the 1–250 µg mL^?1 concentration range. Data indicated that IVM and ivomec® exert both genotoxicity and cytotoxicity in insect cells in vitro, at least in A. albopictus larvae CCL-126? cells.     

Total cobalt determination in human blood and synovial fluid using inductively coupled plasma-mass spectrometry: method validation and evaluation of performance variables affecting metal hip implant patient samples

Inductively coupled plasma with mass spectrometric detection (ICP-MS) has been used for clinical analysis of cobalt (Co) due to its sensitivity and specificity; however, media-specific validation studies are lacking. This study provides data on performance variables affecting differences between selected analytical platforms (Perkin Elmer and Agilent), tissue sample preparation, storage, and interferences affecting measurements in whole blood, serum, and synovial fluid. The limits of detection (LOD) range from 0.2–0.5 µg/L in serum and synovial fluid, and 0.6–1.7 µg Co/L in whole blood. The Agilent platform with collision reaction cell is more sensitive, while the Perkin Elmer platform with dynamic reaction cell demonstrates more polyatomic interferences near the LOD for serum and whole blood. Split sample analysis showed good accuracy, precision, and reproducibility between serum Co measurements using acid digestion or detergent dilution preparations for persons with metal hip implants or following supplement intake. The results demonstrated reliability of the ICP-MS methodology across the two analytical platforms and between two commercial laboratories for Co concentrations above 5 µg Co/L, but digestion procedures and polyatomic interferences may affect measurements in some media at lower concentrations. These studies validate the described ICP-MS methodology for clinical purposes with precautions at low cobalt concentrations (<5 µg Co/L).     

Determination of cobalt by air-assisted liquid–liquid microextraction

Abstract

A rapid and selective technique for extraction, preconcentration and determination of trace amounts of cobalt in water and pharmaceutical samples by air-assisted liquid–liquid microextraction combined with flame atomic absorption spectrometry is proposed. 1-Nitroso-2-naphthol is used as a complexing agent and 1-octanol as an extraction solvent. Parameters relevant for analytical effectivity, i.e. pH of sample solution, concentration of complexing agent, volume of extraction solvent, and number of extraction cycles are optimized using a Box–Behnken design. At optimum conditions, a dynamic linear range of 5–600?µg L^?1 is obtained, with a limit of detection of 1.2?µg L^?1. The method is used for determination of Co(II) in environmental water and pharmaceutical samples.     

Subacute chlorpyrifos-induced alterations in serum lipids and some oxidative stress biomarkers in male Wistar rats: beneficial effect of acetyl-L-carnitine

The present study evaluated the beneficial effect of acetyl-L-carnitine (ALC) on subacute chlorpyrifos (CPF)-induced alterations in serum lipid profiles and some biomarkers of oxidative stress in Wistar rats. Twenty-eight adult male rats divided into four groups of seven animals each (group I–IV) were used: I (S/oil) received soya oil (2 ml kg^?1), II (ALC) received ALC (300 mg kg^?1); III (CPF) received CPF (8.5 mg kg^?1 ～ 1/10th LD₅₀); IV (ALC+CPF) was pretreated with ALC (300 mg kg^?1) and then exposed to CPF (8.5 mg kg^?1), 30 min later. The treatment was orally for 28 days duration. Sera obtained from blood samples were evaluated for the levels of triglyceride (TG), total cholesterol (TC), high density lipoprotein-cholesterol (HDL-c), malondialdehyde (MDA), and the activities of superoxide dismutase (SOD) and catalase (CAT). The levels of low density lipoprotein-cholesterol (LDL-c), very low density lipoprotein-cholesterol (VLDL-c), and atherogenic index (AI) were calculated. The result showed that elevated levels of TG, TC, LDL-c, VLDL-c, AI, and MDA, and the decreased levels of HDL-c, CAT, and SOD induced by CPF were modulated by ALC. It was concluded that ALC ameliorated the alterations in serum lipid and oxidative stress induced by CPF exposure in the rats, partly through its antioxidant properties.     

Accumulation of lead and cadmium by four tropical forage weeds found in the premises of an automobile battery manufacturing company in Nigeria

The potentials of tropical weeds namely, Nephrolepis biserrata, Panicum maximum, Eleusine indica, and Chromolaena odorata to accumulate lead (Pb) and cadmium (Cd) from soil within the premises of an automobile battery manufacturing company in Ota, south-western Nigeria, were explored. The weed samples were collected in both wet and dry seasons. Standard analytical methods were employed to collect, digest, and analyze the weeds. Lead levels in the weeds for both seasons ranged from 1990–4870, 1090–1730, 4800–7890, and 400–1210 µg g^?1 dry weight (DW) for Nephrolepis biserata, Panicum maximum, Eleusine indica, and Chromolaena odorata, respectively, while the cadmium level in the weeds for both seasons ranged from 3.92–6.78 µg g^?1 DW for N. biserata, 1.99–6.85 µg g^?1 DW for P. maximum, 2.90–7.40 µg g^?1 DW for E. indica, and 2.90–5.09 µg g^?1 DW for C. odorata. There was no significant difference in the accumulation of both Pb and Cd for the two seasons. All the weeds showed Pb levels higher than the phytotoxic range. On the contrary, 99% of the weeds showed Cd concentration within the phytotoxic range. The weeds demonstrate good phytoremediation potentials of contaminated soil.     

Spectrophotometric and HPLC method for quantification of Loratadine on swabs for cleaning validation

Cleaning validation is a major challenge in multi-product pharmaceutical industries. UV spectrophotometric and HPLC methods have been developed and validated for determination of residual amount of Loratadine. Both methods were validated for linearity, range, accuracy, precision, and robustness. The limit of quantification was 1 mg L^?1 by UV spectrophotometric method and 0.5 mg L^?1 by HPLC method. A spike recovery study was done on a stainless steel (316 grade) plate and specific residual cleaning level (SRCL) was down to 6 μg 25.8 cm^?2. Recovery was found to be more than 70%. Both methods were simple, highly sensitive, precise, and accurate, and have potential of being useful for routine quality control.     

A novel ligand for cloud point extraction to determine gold content in ore samples

Gold is a valuable metal occurring usually at very low concentrations in complex natural samples. Gold analysis thus needs preconcentration methods. Classical liquid–liquid extraction involves hazardous organic solvents. Alternatively, cloud point extraction involves non-toxic and nonvolatile surfactants. Here, we analyzed ore samples. The complex of Au(III) with sulphapyridylazo resorcin was extracted by the cloud point method. Concentrations were measured by flame atomic absorption spectrometry. We tested the effects of pH, reagent concentration, Triton X-100 surfactant concentration, equilibration temperature and time. Results show that the best detection limit of the method was 0.48 µg L^?1 for Au with a preconcentration factor of 31 times. Calibration is linear in range of 6.4–2,000 µg L^?1, and relative standard deviations are lower than 5 %. Quantum chemical computations reveal the plausible structure of the gold–ligand complex. This report represents the first determination of gold using sulphapyridylazo resorcin as a ligand.     

Elemental composition of particulate matters around Urmia Lake,Iran

Atmospheric particulate matters and their elements were concurrently measured at two sites located in the north and southeast parts of Urmia Lake from January to September 2013. At both sampling sites, average concentrations of total suspended particulate, particles with the aerodynamic diameter of smaller than 10 µm, smaller than 2.5 µm, and smaller than 1 µm were 260 ± 106, 180 ± 73, 30 ± 8, and 25 ± 7 µg m^?3, respectively. The analyzed water soluble ions accounted for approximately 11%–13% mass concentrations of total suspended particulate and 8%–9% of particles smaller than 10 µm, and the sum of the concentrations of the analyzed elements associated with both ranged from 9 to 41 µg m^?3 (6.5%–9.6% in mass) and 7 to 26 µg m^?3 (5.5%–11.3% in mass), respectively. Thus, particulate matter was composed of a complex mixture of minerals such as halite, quartz, gypsum, hexahydrite, and Bassanite.     

Distribution,geochemistry, and mineralogy of aerosols in the Angouran Mine area,northwest Iran

The Angouran Mine, located in northwest Iran, is the largest Zn–Pb producer in the Middle East. This study was designed to investigate the distribution, geochemistry, and mineralogy of the aerosols in the mining area and to assess their likely health impacts on the local residents. For this purpose, 36 aerosol samples were collected from 2014 to 2015 at nine sites located in mine district and upwind and downwind directions. The concentration of potentially toxic elements in the aerosols was determined using AAS instrument. Size, morphology, and mineralogy of the particles were studied using SEM and EDX spectra. The results indicate that the amount of total suspended particles in upwind, mine district, and downwind sites is 95.5, 463.4 and 287.5 µg/m³, respectively. The concentrations of PM_2.5 in the three locations are 8.9, 134.7, and 51.8 µg/m³, whereas the PM₁₀ contents are 2.9, 74.4, and 15.5 µg/m³, respectively. These observations point to the impact of mining activities on the concentration of aerosols in the local atmosphere. The values of air quality index also show the probable effects of the mining activities on the health of the local populations, especially for allergic peoples. The average concentration of Zn in the samples collected from the mining district (290 µg/kg) is much higher than its value in the upwind sites (27 µg/kg). The highest concentration of As (70 µg/kg), Cd (10 µg/kg), and Pb (3 µg/kg) is in downwind sites, which shows the negative impact of mining activities on the local air quality. Temporally, the highest concentration of the studied elements is recorded in spring season, especially for PM_2.5 collected in downwind stations. Based on the results of SEM and EDX spectra, three groups of minerals, i.e., carbonates, silicates, and sulfides, are present in the aerosol particles, confirming the local source for the aerosols. SEM analyses showed that the aerosol particles with dissimilar chemical composition have different morphologies such as irregular, rounded, elongated, and angular. On the basis of the results, the mining activities in the Angouran Zn–Pb Mine may have various short- and long-term consequences on the public health, especially due to high amount of the finer particles (PM_2.5) and the higher concentration of the potentially toxic elements in PM_2.5 which can penetrate into the lungs.