Comparison of sample digestion procedures for the determination of trace elements in antarctic krill by GF‐AAS

Two independent digestion procedures for Antarctic krill samples were compared. Dry ashing (DA) and microwave (MW) acid‐assisted digestion were tested for decomposing the samples to determine essential (Cu, Fe, Cr) and toxic elements (Cd, Pb) by graphite furnace‐atomic absorption spectrometry (GF‐AAS). A mixture of HNO₃ and H₂O₂ as digesting agent was used in the microwave procedure. For the dry ashing digestion, the organic matter was oxidated at 480°C in an open system. Both digestion methods were compared in terms of accuracy and applied to the analysis of a certified reference material: MURST‐ISS‐A2 (Antarctic krill).

The detection limits for the five elements analysed ranged from 3 to 150 ng g^‐1. Both digestion procedures are suitable for the decomposition of krill samples. However, dry ashing is not recommended to determine Pb and Cd because losses can occur.     

Fractionation of Heavy Metals in Surface Sediments of Taihu Lake, East China

The BCR (European Communities Bureau of Reference) three-step sequential extraction procedure was applied to fractionate heavy metals in the sediment of Taihu Lake. For the determination of total metal concentration of the sediments, sample digestion was achieved by using HF/H₂O₂/HNO₃(2/1/1) acid mixture in a microwave-irradiated closed vessel system. The concentrations of Cd, Ni, Cr, Zn, Cu and Pb in various extracts solutions were analyzed by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). The results obtained from the BCR three-step sequential extraction indicated relatively high mobility of Zn, Cu, Pb and Ni in the sediments while Cd and Cr were poorly mobile. Enrichment of heavy metals was found in the sediments collected in the northern parts of Taihu Lake. In the sediments collected in the southern and western sides of the Lake, heavy metal concentrations were relatively low. The relationship between total organic carbon (TOC) and heavy metals concentrations in the sediments is discussed.     

The role of sample preparation in interpretation of trace element concentration variability in moss bioindication studies

Trace element concentrations in plant bioindicators are often determined to assess the quality of the environment. Instrumental methods used for trace element determination require digestion of samples. There are different methods of sample preparation for trace element analysis, and the selection of the best method should be fitted for the purpose of a study. Our hypothesis is that the method of sample preparation is important for interpretation of the results. Here we compare the results of 36 element determinations performed by ICP-MS on ashed and on acid-digested (HNO₃, H₂O₂) samples of two moss species (Hylocomium splendens and Pleurozium schreberi) collected in Alaska and in south-central Poland. We found that dry ashing of the moss samples prior to analysis resulted in considerably lower detection limits of all the elements examined. We also show that this sample preparation technique facilitated the determination of interregional and interspecies differences in the chemistry of trace elements. Compared to the Polish mosses, the Alaskan mosses displayed more positive correlations of the major rock-forming elements with ash content, reflecting those elements’ geogenic origin. Of the two moss species, P. schreberi from both Alaska and Poland was also highlighted by a larger number of positive element pair correlations. The cluster analysis suggests that the more uniform element distribution pattern of the Polish mosses primarily reflects regional air pollution sources. Our study has shown that the method of sample preparation is an important factor in statistical interpretation of the results of trace element determinations.     

Photochemical indicators of ozone sensitivity: application in the Pearl River Delta,China

Surface O₃ production has a highly nonlinear relationship with its precursors. The spatial and temporal heterogeneity of O₃-NO _x -VOC-sensitivity regimes complicates the control-decision making. In this paper, the indicator method was used to establish the relationship between O₃ sensitivity and assessment indicators. Six popular ratios indicating ozone-precursor sensitivity, HCHO/NO _y , H₂O₂/ HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z , were evaluated based on the distribution of NO_x- and VOC-sensitive regimes. WRF-Chem was used to study a serious ozone episode in fall over the Pearl River Delta (PRD). It was found that the south-west of the PRD is characterized by a VOCsensitive regime, while its north-east is NO _x -sensitive, with a sharp transition area between the two regimes. All indicators produced good representations of the elevated ozone hours in the episode on 6 November 2009, with H₂O₂/HNO₃ being the best indicator. The threshold sensitivity levels for HCHO/NO_y, H₂O₂/HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z were estimated to be 0.41, 0.55, 10.2, 14.0, 19.1, and 0.38, respectively. Threshold intervals for the indicators H₂O₂/HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z were able to identify more than 95% of VOC- and NO _x -sensitive grids. The ozone episode on 16 November 16 2008 was used to independently verify the results, and it was found that only H₂O₂/HNO₃ and H₂O₂/NO _z were able to differentiate the ozone sensitivity regime well. Hence, these two ratios are suggested as the most appropriate indicators for identifying fall ozone sensitivity in the PRD. Since the species used for indicators have seasonal variation, the utility of those indicators for other seasons should be investigated in the future work.

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A comparative evaluation of wet digestion and dry ashing methods for the determination of some major and minor nutrients in composted manure

The analytical results of 53 manure samples determined by wet digestion and dry ashing procedures were compared in order to evaluate their relative suitability for recovering different nutrient elements in manure and manure compost. Wet digestion recovered greater amounts of phosphorus (P), potassium (K), calcium (Ca), manganese (Mn), and zinc (Zn) in more samples than dry ashing. Nutrient contents in the samples were highly variable, with coefficients of variation (CV) ranging from 38% for magnesium (Mg) to 161% for copper (Cu) analyzed by the wet digestion procedure, and from 47% to 138% for Mg and Cu analyzed by the dry ashing procedure. The mean values of P, K, Ca, Mn, and Zn averaged for the 53 samples were significantly higher using wet digestion than dry ashing procedure, but both procedures recovered comparable amounts of iorn (Fe), Mg, and Cu. Correlations analysis between both procedures for each element showed reasonable to fair agreements for Ca (R ²?=?0.93), K (R ²?=?0.93), P (R ²?=?0.90), Mg (R ²?=?0.84), Fe (R ²?=?0.87), Mn (R ²?=?0.73), and Cu (R ²?=?0.66), but poor agreement for Zn (R ²?=?0.44). The low agreement between procedures for Zn suggests that wet digestion, which gave a higher recovery, should be a preferred procedure for analyzing Zn in manures.     

Determination of the levels of selected metals in seeds,flowers and fruits of medicinal plants used for tapeworm treatment in Ethiopia

The level of accumulation of selected essential and non-essential metals, namely; Ca, Cu, Fe, Zn, Mn, Cd, Pb, and Cr have been investigated in the seeds, fruits, and flowers of some medicinal plants utilized for tapeworm treatment in Ethiopia and their respective soil samples. These include seed of Cucurbita maxima (Duba), fruit of Embelia abyssinica (Ankoko), flowers of Hagenia abyssinica (Kosso), and fruits of Rosa abyssinica (Kega) and their respective soil samples. A wet digestion procedure with a mixture of conc. HNO₃ and HClO₄ for the plant samples and a mixture of conc. HNO₃, HCl, and H₂O₂ for soil samples were used to solubilize the metals. Ca (1280–12,670?mg?kg^?1) was the predominant metal followed by Fe (104–420?mg?kg^?1), and Zn (18–185?mg?kg^?1) in all the plant materials except for Hagenia abyssinica flower from Hirna in which Mn (16–42?mg?kg^?1) followed by Fe. Among the non-essential toxic metals, Pb was not detected in Cucurbita maxima of Boji, Gedo and Hirna origins and in Rosa abyssinica of Hirna site. Similarly, Cr was not detected in Rosa abyssinica fruits of Boji and Gedo sites. The sampled soils were found to be between strongly acidic to weakly basic (pH: 4.7–7.1). In the soil samples, Ca (8528–18,900?mg?kg^?1) was the most abundant metal followed by Fe (417–912?mg?kg^?1), Zn (155–588?mg?kg^?1), Mn (54–220?mg?kg^?1), Cr (21–105. mg?kg^?1), Cu (11–58?mg?kg^?1), Pb (13–32?mg?kg^?1) and Cd (2.8–4.8?mg?kg^?1). The levels of most of the metals determined in the medicinal plants and the respective soil samples are in good agreement with those reported in the literature and the standards set for the soil by various legislative authorities.     

Removal of Eu3+, Ce3+, Sr2+, and Cs+ ions from radioactive waste solutions by modified activated carbon prepared from coconut shells

As a biomass agricultural waste material, coconut shells were used for the preparation of high-quality modified activated carbon. Chemical modification of the surface of the prepared activated carbon is done by oxidation using H₂O₂ and HNO₃, respectively. The surface area and pore volume of the coconut shells activated carbon are increased by the chemical modification, and followingly the removal of the metals is improved. The structural morphology and composition of the modified activated carbon coconut shells (MACCS) were evaluated by Fourier transform infrared (FTIR) spectra, thermogravimetric analysis–differential thermal analysis (TGA-DTA), scanning electron microscope (SEM), X-ray diffraction (XRD), surface area analysis (SAA), X-ray fluorescence (XRF), and carbon, hydrogen, nitrogen, and sulfur (CHNS) elemental analysis. The prepared MACCS has reasonably good chemical stability. The influence of solution pH, contact time, adsorbent dosage, adsorption temperature, initial metal concentrations, and interfering ions on the adsorption performance of the investigated ions onto the prepared sorbent was examined by a batch method. The selectivity sequence for sorption of Eu³⁺, Ce³⁺, Sr²⁺, and Cs⁺ ions on MACCS was found to be Eu^3+?>?Ce^3+?>?Sr^2+?>?Cs⁺. The saturation capacities of MACCS for the studied metal ions were found to be 136.84, 85.55, 69.85, and 60.00?mg?g^?1 for Eu³⁺, Ce³⁺, Sr²⁺, and Cs⁺ ions, respectively. The thermodynamic parameters, ΔH°, ΔS°, and ΔG° were also evaluated.     

Estimation of the amount of dry deposition in an urban area (Kobe city, Japan) by the inferential method

The amount of dry deposition of SO₂(g) and HNO₃(g) in an urban area in Japan has been estimated by the inferential method. The mean annual dry deposition of SO₂(g) (2.91 kgS/ha/year) was close to or less than that in the Clean Air Status and Trends Network (CASTNet) of the U.S. (3.59 kgS/ha/year). The mean annual dry deposition of HNO₃(g) (10.8 kgN/ha/year) was approximately six times larger than that in CASTNet (1.85 kgN/ha/year). The proportions of dry/(dry+wet) deposition for sulfur and nitrogen were 0.301 and 0.785, respectively.     

Assessment of heavy metals contamination in soils surrounding a gold mine: comparison of two digestion methods

This study investigated two digestion methods (USEPA 3051: microwave, HNO₃ or Hossner: hot plate, HF–H₂SO₄–HClO₄) for heavy metals analysis in contaminated soil surrounding Mahad AD'Dahab mine, Saudi Arabia. Moreover, contamination metal levels were estimated. The Hossner and USEPA 3051 methods showed, respectively, average total contents of 17.2 and 18.1 mg kg^?1 for Cd, 11.6 and 10.6 mg kg^?1 for Co, 45.7 and 34.7 mg kg^?1 for Cr, 1030 and 1100 mg kg^?1 for Cu, 33,300 and 27,400 mg kg^?1 for Fe, 963 and 872 mg kg^?1 for Mn, 33.2 and 22.8 mg kg^?1 for Ni, 791 and 782 mg kg^?1for Pb, and 6320 and 2870 mg kg^?1 for Zn. A lack of significant differences and a high correlation coefficient (>90%) for Cd, Pb and Cu between the two digestion methods suggest that the total-recoverable method (USEPA 3051) may be equivalent to the total-total digestion method (Hossner) for determining these metals in the studied soil. However, significantly higher concentrations of Cr, Fe, Ni and Zn were found by the Hossner method comapred with the USEPA 3051 method. The soil samples have very or extremely high levels of Zn, Cu, Cd and Pb contamination, indicating very high potential ecological risk.     

Inorganic and methyl-mercury speciation in sediments of the Swarzędzkie Lake

Sediment samples were analysed for mercury and methylmercury content in different parts of the bottom sediment of Swarz ?dzkie Lake, which were influenced by different external pollution sources. The results of determination with two methods of mineralization using two separate media (HNO₃/H₂O₂ and HF) were compared. The accuracy of the studied methods was analysed using certified reference material IAEA 405 of river sediment. The recovery of mercury was satisfactory and ranged from 97.5 to 98.8%. Methylmercury compounds in the studied sediments were found in limited concentrations. Their concentrations ranged from 0.26 to 58.1 μg kg^?1, i.e. 1.0–7.4% of the total mercury content. The depth profile displayed high values of both total and methylmercury content at a depth of 10–20 cm, related to the heavy pollution of the lake in the 1980s. Canonical analysis displayed the relationship of both total mercury and methylmercury concentrations with organic matter and phosphorus content in bottom sediments.     

Validation of a digestion procedure for ICP-AES and dynamic reaction cell ICP-MS for trace elemental analysis in environmental samples

Due to chloride polyatomic interferences, hydrochloric acid is not recommended for preparation of samples analysed by ICP-MS and separate digestion procedures are used for ICP-MS and ICP-AES. Here we demonstrate that a single digestion procedure using a mixture of HNO₃ and HCl can be used for ICP-AES and dynamic reaction cell (DRC)-ICP-MS. Hotplate, block digester and microwave digestion were investigated. For a quantitative recovery of 26 elements including Ag, Sb and Ti from waters, soils and sediments, the final concentration of 10% (v/v) HCl in the digest is required regardless of the digestion techniques. The method detection limits of 0.3–1.2 μg/L were obtained for chloride-interfering elements As, V, Cr and Se by DRC-ICP-MS using ammonia and oxygen as the DRC gas.     

Enhanced heterogeneous Fenton-like activity by Cu-doped BiFeO<Subscript>3</Subscript> perovskite for degradation of organic pollutants

Heterogeneous Fenton-like reaction has been extensively investigated to eliminate refractory organic contaminants in wastewater, but it usually shows low catalytic performance due to difficulty in reduction from Fe(III) to Fe(II). In this study, enhanced catalytic efficiency was obtained by employing Cu-doped BiFeO₃ as heterogeneous Fenton-like catalysts, which exhibited higher catalytic performance toward the activation of H₂O₂ for phenol degradation than un-doped BiFeO₃. BiFe_0.8Cu_0.2O₃ displayed the best performance, which yielded 91% removal of phenol (10 mg L^–1) in 120 min. The pseudo first-order kinetic rate constant of phenol degradation in BiFe_0.8Cu_0.2O₃ catalyzed heterogeneous Fenton-like reaction was 5 times higher than those of traditional heterogeneous Fenton-like catalysts, such as Fe₃O₄ and goethite. The phenol degradation efficiency could still reach 83% after 4 cycles, which implied the good stability of BiFe_0.8Cu_0.2O₃. The high catalytic activity of BiFe_0.8Cu_0.2O₃ was attributed to the fact that the doping Cu into BiFeO₃ could promote the generation of Fe(II) in the catalyst and then facilitate the activation of H₂O₂ to degrade the organic pollutants.

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Study on degradation process of famotidine hydrochloride in aqueous samples

The kinetics of famotidine (FAM) transformation under the influence of various factors, important from the environmental point of view, was investigated in aqueous solutions. The degradation processes using UV, H₂O₂, UV/H₂O₂, H₂O₂/Fe²⁺, and UV/H₂O₂/Fe²⁺ were studied. Direct photolysis and H₂O₂-assisted photolysis showed a pseudo-first-order kinetics, while the Fenton and the photo-Fenton processes fit second-order kinetics. The provided experiments proved a high resistance of FAM to direct photolysis. Its stability depends highly on the pH of the reaction solutions. The rate of FAM direct photolysis in acidic solutions was almost negligible. The reaction rate of FAM photolysis at pH 8–9 was 3.7 × 10^?3 min^?1 with DT₅₀ about 3 h 7 min. It was found that the presence of H₂O₂ in the reaction environment enhances the rate of photolysis of FAM. The observed rates of reaction were 5.1 × 10^?3 min^?1 and 3.7 × 10^?3 min^?1 in acidic and basic solutions, respectively. The used Fenton systems appeared to be the most efficient in FAM removal. The rate of reaction depends on concentration of Fe²⁺ and H₂O₂. It was observed that the presence of UV-light enhances the reaction rate by two to six times in comparison to the classical Fenton system. Additionally, FAM behavior in natural water under solar irradiation was examined. The irradiation experiments were carried out in batch experiments with simulated sunlight.     

Sonocatalytic degradation of tetracycline antibiotic in aqueous solution by sonocatalysis

Tetracycline (TC), one of the most common antibiotics, is often poorly bio-degraded in conventional wastewater treatment plants. In this study, the sonocatalytic degradation of TC was investigated using TiO₂ nano-particles as catalyst. The effect of pH, initial TC concentrations, reaction times, and H₂O₂ concentrations were evaluated. The efficacy of ultrasonic irradiation alone in the removal of this pollutant was negligible but removal efficiency increased upon addition of TiO₂ up to 250 mg L^?1; increase of pH and initial TC concentration attenuated TC degradation. Addition of H₂O₂ raised the removal efficiency so that complete removal of TC was achieved within 75 min.     

Effects of three different nanoparticles on bioaccumulation,oxidative stress,osmoregulatory, and immune responses of Carcinus aestuarii

Abstract

In this study, the toxicity of CuO (40?nm), α-Al₂O₃ (40?nm), and α-Fe₂O₃ (20–40?nm) nanoparticles was comparatively investigated on Carcinus aestuarii. Crabs were semi-statically exposed to 1?mg/L of each for 14?days and their accumulation and distribution in tissue and hemolymph, potential oxidative stress mechanism, total hemocyte counts and types, and the osmoregulatory and ionoregulatory responses were determined. The tissue distribution of CuO nanoparticles was hepatopancreas?>?hemolymph?≥?gill?> muscle, for α-Fe₂O₃ gill?>?hepatopancreas?>?muscle?> hemolymph, and for α-Al₂O₃ gill?>?muscle?≥?hemolymph?> hepatopancreas. While α-Al₂O₃ and α-Fe₂O₃ NPs, induced lipid peroxidation and changes in antioxidant enzyme activity in the hepatopancreas tissue, the oxidative damage caused by the CuO nanoparticles was minimal. All three nanoparticles, copper in particular, elicit osmoregulatory and ionoregulatory toxicity at this concentration, due to the inhibition of Na⁺, K⁺-ATPase activity in the gill and depletion of hemolymph and carcass ion concentrations.     

Complexation of iron by salicylic acid and its effect on atrazine photodegradation in aqueous solution

The photodegradation of atrazine and the photochemical formation of Fe(II) and H₂O₂ in aqueous solutions containing salicylic acid and Fe(III) were studied under simulated sunlight irradiation. Atrazine photolysis followed first-order reaction kinetics, and the rate constant (k) corresponding to the solution of Fe(III)-salicylic acid complex (Fe(III)-SA) was only 0.0153 h^?1, roughly one eighth of the k observed in the Fe(III) alone solution (0.115 h^?1). Compared with Fe(III) solution, the presence of salicylic acid significantly enhanced the formation of Fe(II) but greatly decreased H₂O₂ generation, and their subsequent product, hydroxyl radical (˙OH), was much less, accounting for the low rate of atrazine photodegradation in Fe(III)-SA solution. The interaction of Fe(III) with salicylic acid was analyzed using Fourier-transform infrared (FTIR) spectroscopy and UV-visible absorption, indicating that Fe(III)-salicylic acid complex could be formed by ligand exchange between the hydrogen ions in salicylic acid and Fe(III) ions.     

Elemental Contamination of Rainwater by Airborne Dust in Tamale Township Area of the Northern Region of Ghana

Rainwater samples were collected from Tamale town in the 1997 and 1998 rainy seasons. During this period road construction in the Tamale area resulted in the generation of suspended dust in the atmosphere. Analysis of the samples for major ions showed elevated levels of Cl^–. Ion ratios with Cl^– (Na⁺/Cl^–, K⁺/Cl^–, Ca²⁺/Cl^–/Cl^– Mg²⁺/Cl^– and SO₄ ^2–/Cl^–) in rainwater samples were higher than the corresponding ratios in seawater. Some samples also showed elevated concentrations of Fe, Mn, Al and Zn, all of which except Zn showed a correlation with the dry periods between rainfall events. Consequently, it was concluded that dust generated from lateritic soils was probably the major cause of the increase in concentration of these metals. Aluminium and Fe concentrations were observed to be higher than the World Health Organization drinking water guide limits.     

A study on the landfill leachate and its impact on the groundwater quality of the greater area

Characterisation of the leachate originating from the Ano Liosia landfill (situated in Attica region, Greece) as well as assessment on the quality of the local aquifer were carried out. The experimental results showed that most of the parameters examined in the leachate samples such as colour, conductivity, TS, COD, NH₃–N, PO₄–P, SO₄ ^2–, Cl^–, K⁺, Fe and Pb were found in high levels. The organic load was quite high since the COD concentrations were in the range of 3250–6125mgL^–1. In addition, the low BOD/COD ratio (0.096–0.195), confirmed that the majority of this organic matter is not easily biodegradable. The groundwater near the landfill site was characterised as not potable and not suitable for irrigation water, since most of the physical and chemical parameters examined – such as colour, conductivity, DS, hardness, Cl^–, NH₃–N, COD, K⁺, Na⁺, Ca²⁺, Fe, Ni and Pb exceeded the permissible limits given by EE, EPA and the Greek Ministry of Agriculture. Furthermore, this study presents the application of the hydrologic evaluation of landfill performance (HELP) model for the determination of the yearly leakage from the base of the landfill after the final capping.     

Assessment of Young Dong tributary and Imgok Creek impacted by Young Dong coal mine,South Korea

An initial reclamation of the Young Dong coal mine site, located in northeastern South Korea, was completed in 1995. Despite the filling of the adit with limestone, acid rock drainage (ARD) enters Young Dong tributary and is then discharged to Imgok Creek. This ARD carries an average of 500 mg CaCO₃/l of mineral acidity, primarily as Fe(II) and Al. Before spring runoff, the flow of Imgok Creek is 3.3–4 times greater than that of the tributary and has an alkalinity of 100 mg CaCO₃/l, which is sufficient to eliminate the mineral acidity and raise the pH to about 6.5. From April through September 2008, there were at least two periods of high surface flow that affects the flow of ARD from the adit. Flow of ARD reaches 2.8 m³/min during spring runoff. This raised the concentrations of Fe and Al in the confluence with Imgok Creek. However, by 2 km downstream the pH of the Imgok Creek is 6.5 and only dissolved Fe is above the Korean drinking water criteria (0.30 mg/l). This suggests only a minor impact of Young Dong Creek water on Imgok Creek. Acid digestion of the sediments in Imgok Creek and Young Dong Tributary reveals considerable abundances of heavy metals, which could have a long-term impact on water quality. However, several water-based leaching tests, which better simulate the bioavailable metals pool, released only Al, Fe, Mn, and Zn at concentrations exceeding the criteria for drinking water or aquatic life.