Detecting and characterising sources of persistent organic pollutants (PAHs and PCBs) in surface sediments of an industrialized area (harbour of Trieste, northern Adriatic Sea)

A sediment sampling based on a two-dimensional mapping was performed in the harbour of Trieste (northern Adriatic Sea), considering 28 sites exposed to pollutant inputs from harbour and industrial activities. Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were determined in surface sediments, because these very persistent pollutants seem to be responsible for the depletion of benthic populations observed in this area. The correlation matrix indicates that PAHs and PCBs are non-correlated, and probably have different sources. Both cluster analysis performed on the sampling sites and graphical drawing of the PAH sediment contents make it possible to locate along the shoreline a band of more polluted sediments, clustered around a site facing a steelmaking factory, to be considered as the main source point for PAHs. The evaluation of phenanthrene to anthracene (P/AN) and fluoranthene to pyrene (FL/PY) ratios permits the assessment of the pyrolytic, industrial origin of these PAHs, rejecting a second possible source of hydrocarbons (i.e., an oil-pipeline terminal, situated near the steelmaking factory). Graphical drawing of the total PCB iso-concentrations reveals a different source-point for this other category of very persistent pollutants.     

A novel sensor for monitoring leakage of petroleum and other liquid hydrocarbons into soil environments

This paper describes the use of a potentially implantable infrared reflectometer for the qualitative detection of petroleum and a number of other hydrocarbon solvents. A rugged, low-power, re-useable sensor was evaluated in the laboratory for its ability to detect petrol in soil. A hydrophobic fluoropolymer was used as the sensing surface due to its high selectivity for petroleum hydrocarbons. The photocurrent reflected by this surface from a near IR source was measured to test for petroleum saturation within the membrane, which in turn was an indicator of petroleum in the surrounding soil. The simplicity in the sensor design enabled a stable, low cost detection method for petroleum and other hydrocarbons, ideal for use in sub-surface applications.     

Performance evaluation of a sorbent tube sampling method using short path thermal desorption for volatile organic compounds

Air sampling, using sorbents, thermal desorption and gas chromatography, is a versatile method for identifying and quantifying trace levels of volatile organic compounds (VOCs). Thermal desorption can provide high sensitivity, appropropriate choices of sorbents and method parameters can accommodate a wide range of compounds and high humidity, and automated short-path systems can minimize artifacts, losses and carry-over effects. This study evaluates the performance of a short-path thermal desorption method for 77 VOCs using laboratory and field tests and a dual sorbent system (Tenax GR, Carbosieve SIII). Laboratory tests showed that the method requirements for ambient air sampling were easily achieved for most compounds, e.g., using the average and standard deviation across target compounds, blank emissions were < or = 0.3 ng per sorbent tube for all target compounds except benzene, toluene and phenol; the method detection limit was 0.05 +/- 0.08 ppb, reproducibility was 12 +/- 6%, linearity, as the relative standard deviation of relative response factors, was 16 +/- 9%, desorption efficiency was 99 +/- 28%, samples stored for 1-6 weeks had recoveries of 87 +/- 9%, and high humidity samples had recoveries of 102 +/- 12%. Due to sorbent, column and detector characteristics, performance was somewhat poorer for phenol groups, ketones, and nitrogen containing compounds. The laboratory results were confirmed in an analysis of replicate samples collected in two field studies that sampled ambient air along roadways and indoor air in a large office building. Replicates collected under field conditions demonstrated good agreement except for very low concentrations or large (> 41 volume) samples of high humidity air. Overall, the method provides excellent performance and satisfactory throughput for many applications.     

Transportation and fate of cationic surfactant in river water

The degradation, sorption, transportation and material balance of cationic surfactants discharged from domestic waste into river water was studied. Ion-pair solid-phase extraction behavior showed that the sorption of cationic surfactants as an ion-pair with anionic surfactant onto river sediment was so strong that little cationic surfactant was found in the bulk water. Cationic surfactant was found in river sediment at more than 500 times higher concentration than that in the bulk water. The degradation of the cationic surfactant was very slow in river water and much slower in the sediment. A material balance of cationic surfactant was estimated for a river running through Toyama City by measuring the flow rate and the concentration of cationic surfactant in the water at several points. It was found that more than 30% of cationic surfactant introduced to the river was lost during the river running through ca. 3 km in 3 h. This reduction probably comes from a quick transfer of the cationic surfactant from river water to sediment and water weed by means of adsorption or precipitation with suspending solids.     

Human plasma levels of POPs,and diet among native people from Uelen,Chukotka

Some of the people living in the Chukotka Peninsula of Russia depend heavily on marine mammals, but little is known of the exact dietary patterns and plasma levels of POPs among these populations. In this study, POPs levels in plasma from 50 participants from the isolated community of Uelen (Bering Strait) were determined and related to dietary information obtained through a food frequency questionnaire. The intake of marine mammals was high and the combined intake of blubber from walrus, seal and whale was a significant predictor (p < 0.01) of plasma concentrations of sum PCBs and borderline for sum CDs (p = 0.02) and sum DDTs (p = 0.04). There was a significant gender difference in the levels of POPs, and among women there was a significant increase with age. Extensive breastfeeding and lower blubber intake among women could be possible explanations for this gender difference. Despite the high intake of blubber the plasma levels of PCBs and DDTs were lower than some of those reported for the East Coast of Greenland. The geometric mean values for sum PCBs (17 congeners) and sum DDTs were 1316 ng g(-1) lipids and 563 ng g(-1) lipids, respectively. PCB 163, which partly co-eluted with PCB 138, was found in high concentrations (40% of PCB 138). This raises questions regarding the validity of using PCB 138 and PCB 153 to calculate the level of Arochlor 1260. The geometric mean of sum CDs was 518 ng g(-1) lipids. Concentrations of beta-HCH (geometric mean; 410 ng g(-1) lipids) were higher than observed for other native populations depending on marine mammals. Transportation of beta-HCH by ocean currents through the Bering Strait into the Arctic Ocean or regional point sources might explain these elevated levels.     

Chromium redox speciation in natural waters

Dissolved hexavalent chromium concentrations were determined in river, estuarine and coastal waters of the Humber catchment in north-east England. Samples were collected, filtered, extracted on site and after storage for up to eight days. Hexavalent chromium concentrations did not change by more than 0.05 microg l(-1) (not significant, p = 0.05) over this period. Total chromium concentrations in the catchment were less than 1.0 microg l(-1). This is low in relation to the proposed Environmental Quality Standard. Hexavalent chromium accounted for between 27% and 100% of the total dissolved concentration, with an average of approximately 50%. The proportion of Cr(III) and Cr(VI) in the rivers and estuary were of the same range as previously measured in 1993. The addition of Cr(III) and Cr(VI) to fresh and saline water samples illustrates the complexity of the factors controlling chromium speciation in natural waters. The presence of oxidisable organic matter and the stabilising role of complexing organic ligands are proposed as the main controlling influences of redox speciation in filtered samples.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).     

A study of the distribution of lead, cadmium and copper between water and kaolin, bentonite and a river sediment

Experiments were carried out to monitor the equilibrium distribution of lead, cadmium and copper between an aqueous phase modelling natural water and a solid phase modelling natural sediment, under varying conditions. The aqueous phase was analysed using ETAAS and differential pulse anodic stripping voltammetry (DPASV), whereas XRD and FTIR were used to study the solid phase. Sorption isotherms at constant pH were measured. Conditional distribution constants were calculated as functions of the pH, the time of equilibration and the amount of solid material. The results obtained stress the need for standardization of the approaches to the study of water-sediment interactions in order to be able to evaluate and compare the extensive data from field measurements and to predict these interactions.