Survey of concentration of polycyclic aromatic hydrocarbons in lake balaton by HPLC with fluorescence detection

Summary Concentrations of polycyclic aromatic hydrocarbons (PAHs) were determined in water and sediment samples at 15 sites in Lake Balaton during three sampling campaigns in 1996. PAHs were concentrated from water samples by solid phase extraction. Sediment samples were extracted with acetone in an ultrasonic bath then cleaned by solid phase extraction. The total concentration of PAHs ranged from 30–360 ng g⁻¹ and from 170–720 ng L⁻¹ in sediment and water samples, respectively. Spatial and temporal variations of the concentration of PAHs were also investigated. Presented at: Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 3–5, 1997.     

Environmental mobility of trace metals in sediments collected in the Lake Balaton

In environmental pollution studies on solid materials sequential extraction techniques are used for the identification of the main binding sites of trace metals. A four-step sequential extraction procedure was applied to the determination of the distribution of elements like Cd, Cu, As, Pb, Cr, Ni, Zn, Al, Fe, and Mn in sediment samples collected in the Lake Balaton. The fractions were (1) exchangeable and bound to carbonate, (2) bound to Fe/Mn oxide, (3) bound to organic matter and sulfides, and (4) acid-soluble. Elements were mainly accumulated in the stable, acid-soluble fractions. Arsenic and Cd-ions were found in low concentration (1.2–13 mg/kg and < 1 mg/kg, respectively) in the samples. Based on the results determined at 15 sampling points it can be stated that the Lake Balaton has not yet been polluted by the elements investigated.     

Heavy metal inputs in Northern Patagonia lakes from short sediment core analysis

Summary Heavy metal profiles of short sediment cores sampled from lakes located in Nahuel Huapi National Park, Northern Patagonia, Argentina, were determined by INAA. Core dating was performed by measuring natural ²¹⁰Pb and anthropogenic ¹³⁷Cs, and by identification of tephra layers. No evidence was found for the input increase of the trace elements Sb, Ba, Cs, Zn, Co, Hf, Ni, Se, Sr, Ti, U, and V in the lake environment. High As concentrations (up to 250 μg ^. g^-1) were found in relation with the diffusion processes of Mn and Fe oxides. Strong correlation was observed between the Br concentration and organic matter content, but no evidence was found for the relevant increase of Br inputs in recent years. Ag concentrations were found to be enriched in the upper core layers over the baseline values determined for deep layers ranging from 0.1 to 0.2 μg ^. g^-1. Hg concentration profiles were also enriched in the upper core layers over the baseline (from less than 0.07 to 0.2 μg ^. g^-1 for pre-industrial time, to 0.1 to 0.3 μg ^. g^-1 for modern times) but in relation with the increased organic matter content of the sediment.     

Chemical Speciation of Elements in Sediment Samples Collected at Lake Balaton

A modified sequential extraction procedure was applied to determination of the distribution of seven elements (Cd, Cu, As, Pb, Cr, Ni, Zn) in sediment samples collected at Lake Balaton. The fractions were (1) exchangeable and bound to carbonate, (2) bound to Fe/Mn oxide, (3) bound to organic matter and sulfide, and (4) acid soluble. These fractions have the advantage of providing better insight into the mechanism of association of metals with mineralogical phases of the sediments. Samples were taken in three seasons and the average concentration of the elements was calculated. Based on the results determined at 15 sampling points along the lake, it seems that Lake Balaton has not yet been polluted. Concentrations of species were below the Hungarian standard levels set for soils, and most of the elements were found in the acid-soluble fraction, indicating stable compounds in sediments. There were no significant changes in the individual seasonal concentrations of elements in this short monitoring period.     

Multi-element determination with solid sampling by laser ablation using electrothermal atomisation and continuum source coherent forward scattering spectrometry

Laser ablation allows fast and easy sampling of solids with a spatial resolution of some (μm vertical and some 30 μm lateral. The deposition of the laser generated aerosol in a graphite furnace in combination with continuum source CFS allows simultaneous multi-element analysis and the use of internal standards. The aerosol is transported into the graphite furnace with the inert gas flow and deposited by means of a corona discharge inside the tube. The deposition efficiency shows an enhancement by about three orders of magnitude, compared to the deposition without a field. The analytical precision and accuracy has been tested with metals and mineral samples as glassy cinder from a waste incineration plant.     

Behavior of radiocesium in atmospheric arerosol and fallout in Prague

Radiocesium in ground layer atmospheric aerosol and fallout in Prague has been examined. After a decline in 1986–1988, controlled by a sum of two negative exponentials,¹³⁷Cs aerosol concentration reached a constant level based on an equilibrium between its deposition and resuspension. Deposition velocity was compared to that of⁷Be and²²⁶Ra. It confirmed the supposed source of¹³⁷Cs as resuspension from the ground. Resuspension factor of the order of magnitude of 10^–9 was determined, reminding similar values found earlier in Prague as well as those found in Munich. It also agrees well with the USAEC resuspension model. Solubility of¹³⁷Cs was measured in combined wet and dry fallout. The average undissolved fraction of¹³⁷Cs was found to be about 70% which can be explained by the conditions of the¹³⁷Cs aerosol formation in Chernobyl.     

A 110 Year Sediment Record of Polycyclic Aromatic Hydrocarbons Related to Economic Development and Energy Consumption in Dongping Lake,North China

A sedimentary record of the 16 polycyclic aromatic hydrocarbon (PAH) pollutants from Dongping Lake, north China, is presented in this study. The influence of regional energy structure changes for 2–6-ring PAHs was investigated, in order to assess their sources and the impact of socioeconomic developments on the observed changes in concentration over time. The concentration of the ΣPAH₁₆ ranged from 77.6 to 628.0 ng/g. Prior to the 1970s, the relatively low concentration of ΣPAH₁₆ and the average presence of 44.4% 2,3-ring PAHs indicated that pyrogenic combustion from grass, wood, and coal was the main source of PAHs. The rapid increase in the concentration of 2,3-ring PAHs between the 1970s and 2006 was attributed to the growth of the urban population and the coal consumption, following the implementation of the Reform and Open Policy in 1978. The source apportionment, which was assessed using a positive matrix factorization model, revealed that coal combustion was the most important regional source of PAHs pollution (>51.0%). The PAHs were mainly transported to the site from the surrounding regions by atmospheric deposition rather than direct discharge.     

Analysis of BTEX, PAHs and metals in the oilfield produced water in the State of Sergipe, Brazil

During oil and gas exploitation, large amounts of produced water are generated. This water has to be analyzed with relation to the chemical composition to deduce the environmental impact of its discharge after a treatment process. Therefore, a study was carried out to evaluate preliminarily the BTEX (benzene, toluene, ethylbenzene and xylenes), polycyclic aromatic hydrocarbons (PAHs) and metals contents in produced water samples taken from effluents of the Bonsucesso treatment plant located in the city of Carmópolis, the most important oil and gas producer in the State of Sergipe, North-east of Brazil. Three methods were optimized to determine the target compounds. Polycyclic aromatic hydrocarbons were determined by gas chromatography with mass spectrometric detection (GC/MS), volatile aromatic hydrocarbons (BTEX) by gas chromatography with photoionization detector (GC/PID) and metals were analyzed by flame atomic absorption spectrometry (FAAS). The results showed that concentrations of the target compounds in these samples ranged from 96.7 to 1397 μg L^− 1 for BTEX, from 0.9 to 10.3 μg L^− 1 for PAHs and from 0.003 to 4540 mg L^− 1 for metals.     

Heart Failure and PAHs,OHPAHs, and Trace Elements Levels in Human Serum: Results from a Preliminary Pilot Study in Greek Population and the Possible Impact of Air Pollution

Cardiovascular diseases (CVDs) have been associated with environmental pollutants. The scope of this study is to assess any potential relation of polycyclic aromatic hydrocarbons (PAHs), their hydroxylated derivatives, and trace elements with heart failure via their direct determination in human serum of Greek citizens residing in different areas. Therefore, we analyzed 131 samples including cases (heart failure patients) and controls (healthy donors), and the respective demographic data were collected. Significantly higher concentrations (p < 0.05) were observed in cases’ serum regarding most of the examined PAHs and their derivatives with phenanthrene, fluorene, and fluoranthene being the most abundant (median of >50 μg L⁻¹). Among the examined trace elements, As, Cd, Cu, Hg, Ni, and Pb were measured at statistically higher concentrations (p < 0.05) in cases’ samples, with only Cr being significantly higher in controls. The potential impact of environmental factors such as smoking and area of residence has been evaluated. Specific PAHs and trace elements could be possibly related with heart failure development. Atmospheric degradation and smoking habit appeared to have a significant impact on the analytes’ serum concentrations. PCA–logistic regression analysis could possibly reveal common mechanisms among the analytes enhancing the hypothesis that they may pose a significant risk for CVD development.     

Determination of polycyclic aromatic hydrocarbons (PAHs) from organic aerosols using hollow fiber micro-porous membrane liquid-liquid extraction (HF-MMLLE) followed by gas chromatography-mass spectrometry analysis

A method for determination of polycyclic aromatic hydrocarbons (PAHs) from aerosols was developed. Instead of conventionally used non-polar or slightly polar phenylmethylpolysiloxane column a highly polar, highly substituted, cyanopropyl column (VF-23 MS) was used for separation of PAHs. Based on hollow fiber micro-porous membrane liquid-liquid extraction (HF-MMLLE) a method was developed for sample clean up and pretreatment. An enrichment factor of 617-1022 was obtained with extraction efficiency 10.2-18.9% for different PAHs analyzed in this study. The optimized method was successfully applied to aerosol samples and limits of detection between 1.2 pg m⁻³ and 180 pg m⁻³ was obtained. Almost all PAHs were found in most of the aerosol samples.     

Evaluation of combined measurement uncertainty of the determination of Mn content in sediment samples

Combined uncertainties of an analysis of elemental content of sediment samples were evaluated. A monitoring system has been designed and implemented for the characterization of the environmental conditions of Lake Balaton in Hungary. Sediments samples were collected and an acidic digestion method was used to determine the concentration of elements. For the calculation of the result of each measurement three different approaches were considered, namely a.) the calculation of the result using a calibration curve and estimating the confidence limit by the Student t-distribution, b.) calculation of the combined uncertainty and c.) estimation of the sampling errors using the transport and field blanks. The latter approach gave the most reliable result since it included all the parameters which had to be considered regarding sampling and sample handling, and measurement. Determination of acid soluble Mn content in sediment samples has been chosen as an example, and the combined uncertainty is calculated using blanks for sampling. Received: 17 March 2000 Accepted: 4 October 2000     

Determination of copper in medicinal plants used as dietary supplements by atomic absorption spectrometry with direct flame solid analysis

An alternative device for the direct solid analysis (DSA) for copper determination by flame atomic absorption spectrometry (FAAS) is proposed. Copper was directly determined in commercial medicinal plants used as dietary supplements. The determination of copper in solid samples by DSA–FAAS was made by using a conventional air–acetylene flame. Between 0.05 and 1.5 mg of each test, sample was weighed directly into a small polyethylene vial connected to the device used for solid introduction into the flame. Test samples were introduced into the flame as a dry aerosol using a T-quartz cell set between the burner and the optical path. The T-quartz cell has a slit in the superior part by which the solid aerosol passes to the flame. A transient signal, evaluated as integrated absorbance, is produced and it is totally integrated in 2 s. Background signals always presented absorbance values less than 0.1. It was found a characteristic mass of 0.8 ng Cu and absolute limit of detection of 1.2 ng (3 s), or 1.2 μg g⁻¹ if a sample mass of 1 mg was used. Optimized conditions for air flow rate, flame stoichiometry, and so on were established as well. No excessive grinding of the samples was needed and samples with particle of size less than 80 μm were used throughout. No statistical difference between the results from the proposed system and those obtained by sample digestion and determination by conventional FAAS was observed. With the proposed procedure, more than 50 test samples can be analyzed in 1 h and it can be easily adapted to conventional spectrometers for FAAS.     

Distribution of global fallout237Np,Pu isotopes,and241Am in lake and sea sediments

In order to investigate the sedimentary behaviour of neptunium,²³⁷Np together with Pu isotopes and²⁴¹Am have been measured for the sediment cores collected from Lake Mikata (freshwater) and from Lake Kugushi (brakish water) both belonging to the Mikata Five Lakes, and from Nyu Bay (sea water). In all sediment core samples²³⁷Np was detected, and its concentrations were far below those of^239,240Pu and²⁴¹Am measured for the same samples. Inventories of²³⁷Np in Lake Mikata, Lake Kugushi and Nyu Bay were estimated to be 0.53, 0.29 and 0.34 MBq/km², respectively. The activity ratio of²³⁷Np/^239,240Pu calculted from the inventories in each sediment core was 0.29% for Lake Mikata, 0.15% for Lake Kugushi and 0.10% for Nyu Bay. These values except for the value for Lake Mikata are two or three times lower than the value of 0.3–0.4% observed for surface soils of 0–20 cm depth, suggesting that Np is more soluble compared with Pu.     

Homogeneous liquid-liquid extraction combined with gas chromatography-electron capture detector for the determination of three pesticide residues in soils

In this study, a new method was developed for analyzing malathion, cypermethrin and lambda-cyhalothrin from soil samples by using homogeneous liquid–liquid extraction (HLLE) and gas chromatography with electron capture detector (GC–ECD). Acetone was used as extraction solvent for the extraction of target pesticides from soil samples. When the extraction process was finished, the target analytes in the extraction solvent were rapidly transferred from the acetone extract to carbon tetrachloride, using HLLE. Under the optimum conditions, linearity was obtained in the range of 0.05–40 μg kg⁻¹ for malathion, 0.04–10 μg kg⁻¹ for lambda-cyhalothrin and 0.05–50 μg kg⁻¹ for cypermethrin, respectively. Coefficients of correlation (r²) ranged from 0.9993 to 0.9998. The repeatability was carried out by spiking soil samples at concentration levels of 2.5 μg kg⁻¹ for lambda-cyhalothrin, and 10 μg kg⁻¹ for malathion and cypermethrin, respectively. The relative standard deviations (RSDs) varied between 2.3 and 9.6% (n = 3). The limits of detection (LODs), based on signal-to-noise ratio (S/N) of 3, varied between 0.01 and 0.04 μg kg⁻¹. The relative recoveries of three pesticides from soil A1, A2 and A3 at spiking levels of 2.5, 5 and 10 μg kg⁻¹ were in the range of 82.20–91.60%, 88.90–110.5% and 77.10–98.50%, respectively. In conclusion, the proposed method can be successfully applied for the determination of target pesticide residues in real soil samples.     

Fractionation of metals and metalloids by chemical bonding from particles accumulated by electrostatic precipitation in an Argentine thermal power plant

A study was undertaken to evaluate the distribution of Al, As, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn in fly ashes collected in the electrostatic precipitator of a thermal power plant in San Nicolás (Argentina). Five samples were collected during one week of operation. For the fractionation, the scheme applied consisted in extracting the elements in four fractions namely (i) soluble and exchangeable elements; (ii) carbonates, oxides and reducible elements; (iii) bound to sulfidic metals; and (iv) residual elements. Metals and metalloids at μg g^− 1 level were determined in each fraction by inductively coupled plasma optical emission spectrometry (ICP OES). For validation, a standard reference material (SRM 1633 coal fly ash) from NIST was subjected to the same chemical sequential extraction procedure that the samples. X-ray diffraction powder (XRD) analysis and scanning electron microscopy (SEM) were used to characterize the major minerals present in the matrix. Total analyte concentration (in μg g^− 1) varied from 10.6 for Pb to 17,622 for Al. Minimum and maximum concentrations (in μg g^− 1) found in individual samples in the four fractions were: Al, 92.7–9668; As, < 0.3–143; Cr, 2.0–10.4; Cu, < 0.2–35.6; Fe, < 0.3–4992; Mn, < 0.1–128; Ni, < 0.3–139; Pb, < 0.5–9.1; Ti, < 0.3–2243; V, 17.0–112.9; and Zn, < 0.1–68.2. The leachability of the 11 elements under study proved to be different. Low percentages of Al (1%), V (7%) and Cr (8%) were detected in the most bioavailable fraction. Arsenic was found to be most abundant in the non-silicate phase, represented by the second and third fractions, while Cr, Fe, Ni, Pb and Zn were mostly associated to the residual fraction.     

Investigation on Distribution and Risk Assessment of Volatile Organic Compounds in Surface Water,Sediment, and Soil in a Chemical Industrial Park and Adjacent Area

The occurrences, distributions, and risks of 55 target volatile organic compounds (VOCs) in water, sediment, sludge, and soil samples taken from a chemical industrial park and the adjacent area were investigated in this study. The Σ₅₅-VOCs concentrations in the water, sediment, sludge, and soil samples were 1.22–5449.21 μg L⁻¹, ND–52.20 ng g⁻¹, 21.53 ng g⁻¹, and ND–11.58 ng g⁻¹, respectively. The main products in this park are medicines, pesticides, and novel materials. As for the species of VOCs, aromatic hydrocarbons were the dominant VOCs in the soil samples, whereas halogenated aliphatic hydrocarbons were the dominant VOCs in the water samples. The VOCs concentrations in water samples collected at different locations varied by 1–3 orders of magnitude, and the average concentration in river water inside the park was obviously higher than that in river water outside the park. However, the risk quotients for most of the VOCs indicated a low risk to the relevant, sensitive aquatic organisms in the river water. The average VOCs concentration in soil from the park was slightly higher than that from the adjacent area. This result showed that the chemical industrial park had a limited impact on the surrounding soil, while the use of pesticides, incomplete combustion of coal and biomass, and automobile exhaust emissions are all potential sources of the VOCs in the environmental soil. The results of this study could be used to evaluate the effects of VOCs emitted from chemical production and transportation in the park on the surrounding environment.     

Certified reference material for quantification of polycyclic aromatic hydrocarbons in sediment from the National Metrology Institute of Japan

The National Metrology Institute of Japan has issued a certified reference material (CRM) of freshwater lake sediment for polycyclic aromatic hydrocarbon (PAHs) analyses. The certification used three extraction techniques: pressurized liquid extraction (PLE) with toluene, PLE with dichloromethane/ethyl acetate (1:1 by volume), and alkaline extraction (1 M KOH in methanol) in combination with microwave-assisted extraction. Both gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/dopant-assisted atmospheric pressure photoionization/MS (LC/DA-APPI/MS) analyses were used. Certified values are provided for 18 PAHs at 1–25 μg kg⁻¹ except for perylene (2.08 × 10³ μg kg⁻¹), and information values are provided for two. Since the values of PAHs in the CRM are much lower than those in other CRMs and are comparable to those found at sites with little human influence, the CRM is suitable for PAH monitoring in sediment and soil samples.     

The rapid separation of trace metals from neutron-activated saline matrices by chelation on a poly-5-vinyl-8-hydroxyquinoline column

Instrumental neutron activation analysis of biological and environmental samples suffers from interferences caused by high salt concentrations. Poly-5-vinyl-8-hydroxy-quinoline coated on controlled pore diameter glass beads is suggested as a chelating column for the rapid removal of aluminum, vanadium, copper and manganese from neutron-activated sea-water samples. Separation from bulk elements is satisfactory at flow rates of 20 ml min⁻¹. With addition of carriers and with chemical yield determinations, relative standard deviations of 2–10% can be achieved for spike concentrations of 0.1 μg Mn ml⁻¹, 0.3 μg V ml⁻¹, 20 μg Al ml⁻¹ and 1.0 μg Cu ml⁻¹.     

Multivariate optimization and validation studies in on-line pre-concentration system for lead determination in drinking water and saline waste from oil refinery

The present paper proposes an on-line pre-concentration procedure for lead determination in drinking water and saline waste from oil refinery by flame atomic absorption spectrometry (FAAS). It is based on the sorption of lead (II) ions in a minicolumn of polyurethane foam loaded with 4-(2-pyridylazo)-resorcinol (PAR) reagent. The optimization step was performed using Doehlert matrix involving the variables: sampling flow rate (SR), buffer concentration (BC), pH and eluent concentration (EC). The validation process was performed considering the parameters: linearity and other characteristics of the calibration curve, analytical features of on-line system, precision, robustness, effect of other ions in the pre-concentration system and accuracy. Using the established experimental conditions, the procedure allows lead determination with detection limit (3δ/S) of 0.4 μg l⁻¹, quantification limit (10δ/S) of 1.4 μg l⁻¹, and a precision, calculated as relative standard deviation (RSD) of 5.7 (n=8) and 2.1% (n=8) for lead concentration of 5 and 50 μg l⁻¹, respectively. The pre-concentration factor (PF) considering the ratio among the slopes of the analytical curves with and without pre-concentration is 51. The achieved recovery for lead determination in presence of several cations demonstrated that this procedure could be applied for analysis of water samples. The accuracy was confirmed by analysis of the standard reference material NIST 1640 Trace elements in natural water. The sorption process was characterized by the Langmuir isotherm. The method was applied for lead determination in drinking water collected in Salvador City, Brazil and in saline effluent samples from oil refinery. The lead content for 16 samples of drinking water analyzed varied from 0.77 to 6.98 μg l⁻¹.     

Thermophoretic deposition of palladium aerosol nanoparticles for electroless micropatterning of copper

A method for catalytic activation was introduced by producing palladium aerosol nanoparticles via spark generation and then thermophoretically depositing the particles onto a flexible polyimide substrate through a hole in pattern mask, resulting in a line (24 μm in width) and a square (136 μm × 136 μm) patterns. After annealing, the catalytically activated substrate was placed into a solution for electroless copper deposition. Finally, copper micropatterns of a line (35 μm in width) and a square (165 μm × 165 μm) were formed only on the activated regions of the substrate. Both patterns had the height of 1.6 μm.