Technetium-99 in Fucusand seawater samples in the Finnish coastal area of the Baltic Sea, 1999

Liquid discharges of ⁹⁹Tc from the Sellafield nuclear facilities increased largely in the mid 90"s. These releases are transported to the Nordic sea areas by the ocean currents. Results of the ⁹⁹Tc activities along the Norwegian coastal areas and in the North Sea have been reported but then again, the spreading of ⁹⁹Tc into Baltic Sea has not been studied thoroughly. Fucus vesiculosus and seawater samples were collected in the summer 1999 from the Finnish coastal areas for measuring ⁹⁹Tc in the Baltic Sea area. A modified analytical method for measuring ⁹⁹Tc in the environmental samples was developed at that time. The method based on extraction chromatography and liquid scintillation measurement of ⁹⁹Tc. The ⁹⁹Tc concentration in the Fucus vesiculosus in the Finnish coast of the Baltic Sea varied from 1.6 to 11.6 Bq/kg (dry weight) being highest at the most northern sampling sites. These values were considerable lower than those in the Danish and Norwegian coasts. The variation in the concentrations observed are probably due to biological factors. The ⁹⁹Tc concentration in the Baltic Sea water studied was below 0.2 Bq/m³.     

Estimation of the efficiencies and uncertainties of the extraction and cleanup steps of pesticide residue determination in cucumber using <Superscript>14</Superscript>C-carbaryl

The estimation of the uncertainty of measurement has, nowadays, become an integral part of analytical results. The uncertainty and efficiency of extraction and cleanup are very important components of a pesticide residue analytical method. In this work, for a quick review of extraction and cleanup efficiency and to evaluate the individual analysis steps during method adaptation, ¹⁴C-carbaryl was applied at all fortification levels. Then, further analyses, such as ethylacetate extraction, filtration, evaporation and cleanup, were performed. The calibration of gel chromatograph column, performed with both ¹⁴C-carbaryl and fortification mixture (dichlorvos, malathion and chlorpyrifos), showed that pesticide fractions came through the column between the 8- and 23-mL fractions. The overall recovery of ¹⁴C-carbaryl after the extraction and cleanup step was 0.91, with the relative uncertainty of 0.084. Using the “bottom-up” approach, the uncertainty of extraction u _cEX and cleanup u _cGPC were 0.033 and 0.107, respectively. The combined standard uncertainty u _c associated with the described analytical method was 0.112. Similar values were obtained using the alternative “top-down” approach: uncertainty of extraction u _ct1 was 0.039, uncertainty of cleanup u _ct2 was 0.108 and the combined standard uncertainty u _cAV was 0.081. Both approaches showed that the uncertainty of cleanup was the main source of combined standard uncertainty.     

Atmospheric Hydrocarbon Concentrations in the Baltic Sea Area

Abstract

During a marine research expedition in 1983 in the Baltic Sea area air samples were collected for the analysis of several organic and inorganic pollutants. The aim of the expedition was to obtain information on the airborne load in the sea as well as to measure the concentrations of the pollutants far away from source areas. In this paper the background concentrations of the primarily traffic originated aromatic hydrocarbons benzene, toluene and xylenes will be presented.

The concentrations of benzene were from 0.2 to 2μg/m³, of toluene between 0.4–3μg/m³, of m-xylene 0.02–0.60μg/m³ while the concentrations of o-xylene were 0.01–0.1 μg/m³. The concentrations did not depend too much on the origin (continental/sea type) of the air masses. A weak minimum in the concentrations of the measured hydrocarbons was noticed in the central Baltic Sea area. When comparing lead concentrations in fine particles (< 2.5 μm) with those of benzene, toluene and m-xylene some coincidence between them could be observed.     

Acoustical and excess thermodynamic studies of mixtures of 2-pyrrolidone with 1,3-propanediol and water as well as 1,3-propanediol with water at 308.15 K

The density (ρ), viscosity (η) and ultrasonic velocity (u) of three mixtures consisting of 2- pyrrolidone with 1,3-propanediol (PD) and water and also of PD and water have been measured as a function of mole fraction at 308.15 K. The experimentally collected data has been used to calculate the excess molar volume (V^E), deviation in viscosity (Δη), deviation in ultrasonic velocity (Δu), isentropic compressibility (κ_s), deviation in isentropic compressibility (Δκ_s) and excess Gibbs free energy of activation (ΔG*^E). The Redlich–Kister polynomial equation has been used to fit the derived parameters. The variation in excessive thermodynamic properties as a consequence of possible molecular interactions is discussed.     

Uncertainty estimation of ethanol concentration in simulated breath using enzyme-based biosensors

Exhaled breath (EB) contains volatile and nonvolatile compounds that are correlated with physiological processes in the body, and these breath biomarkers hold enormous diagnostic potential when they are adequately measured and monitored. Thus, the development of instrumentation, including enzyme-based biosensors, for breath monitoring applications has been expanding rapidly. In this paper, the process of estimating the overall combined uncertainty in predicting ethanol concentration, u(C _v)_pred, using a calibrated alcohol oxidase-based amperometric biosensor is presented. Components that contributed to u(C _v)_pred were the standard uncertainties associated with simulation of a breath sample with trace ethanol concentration, sampling temperature, biosensor instrumentation, and regression analysis. In both EB and exhaled breath condensate (EBC) sensing, the largest contributor to overall uncertainty was the random effects captured by the regression model at 38.2 % and 39.8 %, respectively, for EB and EBC. This was followed by biosensor instrumentation (34.5 %) and simulation (25.3 %) in EB sensing. The trend was reversed in EBC sensing with EB simulation having a larger contribution (33.8 %) than biosensor instrumentation (25.5 %) owing to a better repeatability of amperometric measurements with aqueous samples. The remaining 2.0 % and 0.9 % were due to breath sampling temperatures in EB and EBC sensing, respectively. This study provides a framework for how to incorporate uncertainty estimation in both breath monitoring and is applicable to biosensing of other breath biomarkers.     

Volumetric,viscometric and acoustic properties of binary mixtures of 2-propanol with n -alkanes (C6, C8, C10) at 298.15 and 308.15 K

Densities (ρ), viscosities (η), and speeds of sound, (u) of the binary mixtures of 2-propanol with n-alkanes (n-hexane, n-octane, and n-decane) were measured over the entire composition range at 298.15 and 308.15 K and at atmospheric pressure. Using the experimental values of density, viscosity and speed of sound, the excess molar volumes (V ^E), viscosity deviations (Δη), deviations in speed of sound (Δu), isentropic compressibility (κ _s), deviations in isentropic compressibility (Δκ _s), and excess Gibbs energies of activation of viscous flow (ΔG* ^E) were calculated. These results were fitted to the Redlich–Kister type polynomial equation. The variations of these excess parameters with composition were discussed from the viewpoint of intermolecular interactions in these mixtures. The excess properties are found to be either positive or negative depending on the molecular interactions and the nature of liquid mixtures.     

Determination of uncertainty in analytical measurements from collaborative study results on the analysis of a phenoxymethylpenicillin sample

The correct interpretation of a measurement result requires knowledge about its uncertainty. Depending on the conditions under which the analyst is operating, different operational definitions of uncertainty have been proposed. They include: within-laboratory uncertainty, reproducibility uncertainty, bias-included uncertainty and absolute uncertainty. Here we consider the evaluation of the reproducibility uncertainty derived from the results obtained in an inter-laboratory experiment. Nine laboratories participated in an inter-laboratory study for the analysis of phenoxymethylpenicillin. The analyses consisted of a Karl-Fischer water determination, an acid-base titration to assay phenoxymethylpenicillin and a liquid chromatography (LC) method to determine 4-hydroxyphenoxymethylpenicillin and other impurities. The experimental set-up allowed to obtain for each determination s_r² and s_L² as estimates of the repeatability variance (σ_r²) and the between-laboratory variance (σ_L²), respectively. The reproducibility uncertainties for the different assays were then derived from these estimates.     

Acoustical Properties of Binary Mixtures of Heptane with Ethyl Acetate or Butyl Acetate

Mixed solvents rather than single pure liquids are of utmost practical importance in chemical and industrial processes as they provide an ample opportunity for the continuous adjustment of desired properties of the medium. Therefore, ultrasonic velocity (u) and density (ρ) were measured for the binary mixtures formed by heptane with ethyl acetate or butyl acetate at temperatures 293, 298 and 303 K over the entire composition range. Deviation in ultrasonic velocity (Δu), deviation in isentropic compressibility (Δκ_s), and excess intermolecular free length (L^E_f) have been evaluated using the ultrasonic velocity data and the computed results were fitted to the Redlich‐Kister polynomial equation. The values of Δu, Δκ_s and L^E_f were plotted against the molar fraction of heptane. The observed positive and negative values of excess parameters were discussed in terms of molecular interaction between the components of the mixtures. Experimental values of ultrasonic velocity and density were compared with the results obtained by theoretical estimation procedures. The results were discussed in terms of average absolute deviation (AAD).     

Depth profiles of 129I species in the Bothnian Sea

The Bothnian Sea which is located between Finland and Sweden represents an important source of fresh water to the Baltic Sea. We here present new data on the radioactive isotope ¹²⁹I species from water samples collected in December 2009 at different depths in the Bothnian Sea. Concentrations of ¹²⁹I^? (iodide) in the Bothnian Sea range from 14 × 10⁸ to 32 × 10⁸ atoms/L, while ¹²⁹IO₃ ^? (iodate) concentrations are relatively low and fluctuating at 1 × 10⁸ atoms/L. For nutrients data determined in the same samples as ¹²⁹I, significant correlations could be found between ¹²⁹I^? and total P, NO₃–N, SiO₃–Si, but rather poor with NH₄–N. The correlations suggest comparable source pathway of ¹²⁹I^? and nutrient parameters, while the source of NH₄–N may be different. The small amounts and negligible change of ¹²⁹IO₃ ^? indicate prevailing extensive reduction of iodate in the Baltic Sea.     

Estimating sampling and analysis uncertainties to assess the fitness for purpose of a water quality monitoring network

In order to verify that the protocols used for water quality monitoring of surface waters within the Long-term Environmental Research Monitoring and Testing System (OPE), located in the north-eastern part of France in relation with a geological disposal for radioactive waste project, are fit for purpose, a validation study was conducted following the methodology described in the Eurachem/citac and Nordtest guidance documents on uncertainty arising from sampling. As one of the objectives of the OPE water monitoring programme was to investigate the spatial and temporal variability of water quality, quality requirements were set to having a measurement variance, including sampling and analytical contributions, less than 20 % of the total variance to minimise the impact of measurement over the observed environmental variability. The replicate method was then selected in order to estimate the measurement uncertainty, including the sampling contribution, as well as the spatial and temporal variability of water quality of surface waters. To minimise costs, a single-split level was selected. Analytical uncertainties were assessed from inter-laboratory data and/or internal quality control data from the last 2–5 years. Finally, ANOVA was applied to the data sets after elimination of outliers. Results showed that for pH, electrical conductivity, turbidity and nitrate, the sampling uncertainty was negligible, whereas for other parameters such as dissolved oxygen, total suspend solids, total organic carbon, nitrite and phosphate, the sampling contribution to the measurement uncertainty was largely significant. For all parameters except calcium, the sampling and analytical protocols were considered fit for purpose.     

Bayesian uncertainty quantification of recent shock tube determinations of the rate coefficient of reaction H + O2→ OH + O

We analyze the ignition delay in hydrogen–oxygen combustion and the important chain ‐branching reaction H + O₂→ OH + O that occurs behind the shock waves in shock tube experiments. We apply a stochastic Bayesian approach to quantify uncertainties in the theoretical model and experimental data. The approach involves a statistical inverse problem, which has four “components” as input information: (a) model, (b) prior joint probability density function (PDF) of the uncertain parameters, (c) experimental data, and (d) uncertainties in the scenario parameters. The solution of this statistical inverse problem is a posterior joint PDF of the uncertain parameters from which we can easily extract statistical information. We first perform a parametric study to investigate how the level of the total uncertainty (which we define as the sum of model uncertainty and experimental uncertainty) affects the uncertainty in the rate coefficient k₁ of the reaction H + O₂→ OH + O, which is “most likely” expressed by k₁=1.73×10²³T^?2.5exp(?11550/T) cm³ mol^?1 s^?1 over the experimental temperature range 1100–1472 K. We also introduce the idea of “irreducible” uncertainty when considering other parameters in the system. After statistically calibrating the parameters modeling the rate coefficient k₁, we predict its 95% confidence interval (CI) for different temperature regimes and compare the CI against the values of k₁ obtained deterministically. Our results show that a small uncertainty in gas temperature (±5 K) introduces appreciable uncertainty in k₁. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 586–597, 2012     

Uncertainty Budget for k0-NAA

The concepts of the Guide to the expression of Uncertainties in Measurements for chemical measurements (GUM) and the recommendations of the Eurachem document "Quantifying Uncertainty in Analytical Methods" are applied to set up the uncertainty budget for k ₀-NAA. The "universally applicable spreadsheet technique", described by Kragten, is applied to the k ₀-NAA basic equations for the computation of uncertainties. The variance components — individual standard uncertainties — highlight the contribution and the importance of the different parameters to be taken into account.     

Optimisation of sample pre-treatment method for the determination of triclosan in marine sediments by high-performance liquid chromatography and marine benthic quality assessment in the southern Baltic Sea

This study comprises optimisation of sample preparation and HPLC analytical procedure for the determination of a personal care product ingredient, triclosan (TCS), in marine sediments. The testing of several varying pre-treatment parameters confirmed that ultrasonic extraction is an effective method for the isolation of TCS from marine sediments, and that the choice of extraction solvent appeared to be of major importance. The selection of the mobile-phase composition and the absorption wavelength was made for the high-performance liquid chromatography analysis step. Based on the validated method, a preliminary assessment of the benthic ecosystem quality with regards to TCS contamination has been demonstrated in the southern Baltic Sea – a semi-enclosed sea, characterised by poor water exchange, thus particularly susceptible to anthropopression. TCS has been identified and quantified in situ in marine bottom sediments, sediment dwelling isopod – Saduria entomon L. and estimated in silico in pore waters based on the equilibrium partition theory in order to assess the potential exposure and uptake from the aqueous phase. TCS concentrations identified in the bottom sediments of the Gdansk Basin, as the natural habitat for studied S.entomon L., appear to be threatening to the benthic environment. Particularly when considering S. entomon L. as a major nutrition source for cod (Gadus morhua) undergoing the feminisation process, since the recent studies prove TCS to have a potential to induce critical alterations in the endocrine system of marine ichthyofauna.     

Determination of Volatile Halogenated Compounds in Tap and Surface Waters from the Gdańsk District

Abstract

The present method is based on preconcentration of organic contaminants on XAD-4 as sorbent, thermal desorption, mineralization and coulometric argentometric titration for the final determination of halides. The results were calculated as the total parameter VOX (volatile organic halogen) expressed as chlorine. The method has been used for the VOX determination in tap water, Vistula river water and Baltic Sea water. Sampling of the Baltic Sea water has been carried out during the research cruise of the r/v ‘Oceania’. The relatively high anthropogenic pollution of the river Vistula (c _vox = 11–45 μg Cl/cd³), Gulf of Gdańsk (c _vox = 0.6–4.5 μg Cl/dm³) and the Pomerania Bay (c _vox = 2 μg Cl/dm³) has been determined. The VOX concentration in the tap water varied between 13 and 56 μg/dm³; that is, this water is seriously polluted by volatile organic halogen compounds.     

Thermophysical and thermoacoustical properties of benzaldehyde mixtures with ethylbenzene at 303.15, 308.15, and 313.15 K and a pressure of 0.1 MPa

Ultrasound velocity (u), density (ρ) and viscosity (η) measurements of benzaldehyde + ethylbenzene mixtures have been carried out at 303.15, 308.15, and 313.15 K. These values have been used to calculate the excess molar volume (V ^E), deviation in viscosity (δη), and deviation in isentropic compressibility (δβ_s), deviations in ultrasound velocity (δu), excess free volume (δV _f), excess intermolecular free length (δL _f) and excess Gibbs free energy of activation of viscous flow (δG ^E). McAllister’s three body interaction model is used for correlating kinematic viscosity of binary mixtures. The excess values were correlated using the Redlich-Kister polynomial equation to obtain their coefficients and standard deviations. The thermophysical properties under the study were fit to the Jouyban-Acree model. The observed variation of these parameters helps in understanding the nature of interactions in these mixtures. Further, theoretical values of the ultrasound speed were evaluated using theories and empirical relations.     

Correlation between iodine isotopes (129I and 127I) species and marine parameters in the Baltic Sea

Iodine is a bio-intermediate and redox-sensitive element in the oceans and understanding the relationship between transformation of iodine species promotes them as indicators of biochemical cycling in the ecosystems. To gain an insight into the transformation of iodine species, correlations between the iodine species (¹²⁷IO₃ ^?, ¹²⁷I^?, ¹²⁹I^?, ¹²⁹IO₃ ^?) and marine parameters (temperature, salinity, oxygen, total phosphorus, nitrate and ammonium) are assessed here for the Baltic Sea during different seasons. The datasets used cover the periods of August 2006, April 2007 and November 2009. The results indicate that the correlations between radioactive ¹²⁹I, stable ¹²⁷I species and marine parameters mainly response to their respective sources as well as oceanographic environments. Also, insignificant correlations of iodine species and nutrients data (total phosphorus, nitrate and ammonium) are observed, suggesting that transformation activity of iodine species in the Baltic Sea is not directly linked to biological production.     

Experimental study and modelling of 137Cs sorption behaviour in the Baltic Sea and the Curonian Lagoon

Sorption–desorption behaviour of ¹³⁷Cs in the Baltic Sea and the Curonian Lagoon was studied in 1997–2009 with the aim to better understand processes responsible for redistribution and sink of ¹³⁷Cs in the system. Data obtained from several sampling campaigns were analyzed and short and long-term kinetic tracer experiments using natural water and bottom sediments were carried out with particles of various sizes from 0.2 to 50 μm. Samples of suspended particles and bottom sediments collected during two sampling campaigns were fractionated according to the size, and association of ¹³⁷Cs with solid phase was studied using sequential extraction. The difference in ¹³⁷Cs behaviour observed between expeditions in 1999 and 2001 was attributed to seasonal variations in chemical composition of suspended particles entering the system and consequent differences between the sorption (in 1999) and the desorption (in 2001) of ¹³⁷Cs in sea water. Data obtained from tracer kinetic sorption experiments with ¹³⁴Cs and bottom sediment fractions of different grain size were used for finding a suitable kinetic sorption model, kinetic constants and the corresponding equilibrium K _d values. It has been found that the modelled data best conform to the mechanism of ion diffusion through the so-called inert layer on the surface of the sediment particles.     

Determination of heavy metals in environmental bio-indicators by voltammetric and spectroscopic techniques

The determination of copper, lead, cadmium and zinc in matrices involved in the food chain as algae, species Ulva rigida, and clams, species Tapes philippinarum by differential pulse anodic stripping voltammetry (DPASV) was carried out. For the mercury determination in these matrices, a new accurate and precise method was developed employing a mixture of concentrated acids H₂SO₄-K₂Cr₂O₇ for digestion and subsequent cold vapor atomic absorption spectrometry (CV-AAS) by reduction with SnCl₂. The analytical procedures were verified for four reference standard materials: Ulva lactuca BCR-CRM 279, Lagarosiphon major BCR-CRM 060, Oyster tissue NBS-SRM 1566, Mussel tissue BCR-CRM 278. For all the elements the precision, expressed as relative standard deviation (s_r), and the accuracy, expressed as relative error (e), were in the order of 3 to 5%, while the detection limits were in the range 0.010–0.100 μg/g. The standard addition technique improved the resolution of the voltammetric method even in the case of very high element concentration ratios. The analytical procedure was used for real matrices sampled in the Adriatic Sea south to Po river mouth, in the zone “Goro bay”, and at open sea north to the Ravenna shore. Received: 7 June 1998 / Revised: 2 November 1998 / Accepted: 5 November 1998     

Evaluation of volatile chlorinated hydrocarbons distribution along depth profiles in the Ross Sea, Antarctica

The presence and the distribution along depth profiles of volatile chlorinated hydrocarbons (VCHCs) were evaluated in seawater samples collected in the Ross Sea (Southern Ocean, Antarctica) during the 2002-2003 Italian expedition. Sampling areas were located where the Circumpolar Deep Water interacts with the shelf waters that supply the Ross Sea.The VCHCs investigated were: 1,1,1-trichloroethane (C₂H₃Cl₃), tetrachloromethane (CCl₄), trichloroethylene (C₂HCl₃), tetrachloroethylene (C₂Cl₄). The analytical procedure consisted of a liquid-liquid extraction carried out with n-hexane directly in Antarctica, followed by gas chromatographic analysis with electron capture detection carried out in Italy.Concentration levels for the VCHCs analysed ranged from digits to hundreds of ng/L according to the station, depth and substance considered. Important differences in concentration levels between the three stations near the Ross Ice Shelf and the two stations located in the Cape Adare area were observed. In particular the stations situated in the Cape Adare zone, at certain depths, showed a thermal inversion due to the mixing of the Circumpolar Deep Water with the waters generated inside the Ross Sea Basin. The lowest concentration levels were recorded at this temperature increase.     

Evaluation of measurement uncertainty in the determination of 210Pb and 210Po using beta counting and alpha spectrometry

 Measurement uncertainties in the determination of ²¹⁰Pb and ²¹⁰Po in Reference Material IAEA-300 (Baltic Sea Sediment) were evaluated. ²¹⁰Pb and ²¹⁰Po were separated from the matrix using an Sr resin column. The chemical yield of ²¹⁰Pb was determined gravimetrically in PbSO₄ form. Precipitation was followed by beta proportional counting after ²¹⁰Bi ingrowth. ²¹⁰Po was determined by alpha spectrometry after its spontaneous deposition on a Cu planchet. The major source of uncertainty was identified as the statistical counting uncertainty, which was also expected and is almost impossible to reduce without extension of the time required for an analysis. The expanded uncertainties were determined as 7.4% and 12.2% for ²¹⁰Pb and ²¹⁰Po, respectively. Received: 3 September 2002 Accepted: 3 December 2002 Acknowledgement This work was financially supported by Ministry of Education, Science and Sport, Republic of Slovenia (Project group PO-0106–0532). Presented at CERMM-3, Central European Reference Materials and Measurements Conference: The function of reference materials in the measurement process, May 30–June 1, 2002, Rogaška Slatina, Slovenia Correspondence to P. Vreˇcek