Characterisation of the dilute HCl extraction method for the identification of metal contamination in Antarctic marine sediments

A regional survey of potential contaminants in marine or estuarine sediments is often one of the first steps in a post-disturbance environmental impact assessment. Of the many different chemical extraction or digestion procedures that have been proposed to quantify metal contamination, partial acid extractions are probably the best overall compromise between selectivity, sensitivity, precision, cost and expediency. The extent to which measured metal concentrations relate to the anthropogenic fraction that is bioavailable is contentious, but is one of the desired outcomes of an assessment or prediction of biological impact. As part of a regional survey of metal contamination associated with Australia's past waste management activities in Antarctica, we wanted to identify an acid type and extraction protocol that would allow a reasonable definition of the anthropogenic bioavailable fraction for a large number of samples. From a kinetic study of the 1 M HCl extraction of two Certified Reference Materials (MESS-2 and PACS-2) and two Antarctic marine sediments, we concluded that a 4 h extraction time allows the equilibrium dissolution of relatively labile metal contaminants, but does not favour the extraction of natural geogenic metals. In a regional survey of 88 marine samples from the Casey Station area of East Antarctica, the 4 h extraction procedure correlated best with biological data, and most clearly identified those sediments thought to be contaminated by runoff from abandoned waste disposal sites. Most importantly the 4 h extraction provided better definition of the low to moderately contaminated locations by picking up small differences in anthropogenic metal concentrations. For the purposes of inter-regional comparison, we recommend a 4 h 1 M HCl acid extraction as a standard method for assessing metal contamination in Antarctica.     

Environmental impact of unleaded gasolines in the bay of Cádiz (Spain)

Given the strategic situation of the José León de Carranza bridge, which spans the Bay of Cádiz (in the SW of Spain) and carries very heavy motor traffic, together with knowledge of the currents and tidal flows in the zone, we have used a technique of radioactive dating of sediments to study the temporal evolution presented by contamination from lead in the sediment column. This has allowed us to observe the environmental impact, in terms of the concentration of Pb in the sea bed sediments, that has been produced in the zone by the introduction of unleaded gasolines as substitutes for traditional automobile fuels that employ organic forms of tetra methyl lead as an antidetonant agent in the fuel.     

Correlations in the chemical composition of rural background atmospheric aerosol in the UK determined in real time using time-of-flight mass spectrometry

An aerosol time-of-flight mass spectrometer (ATOFMS) was used to determine, in real time, the size and chemical composition of individual particles in the atmosphere at the remote inland site of Eskdalemuir, Scotland. A total of 51,980 particles, in the size range 0.3-7.4 microm, were detected between the 25th and 30th June 2001. Rapid changes in the number density, size and chemical composition of the atmospheric aerosol were observed. These changes are attributed to two distinct types of air mass; a polluted air mass that had passed over the British mainland before reaching Eskdalemuir, interposed between two cleaner air masses that had arrived directly from the sea. Such changes in the background aerosol could clearly be very important to studies of urban aerosols and attempts at source apportionment. The results of an objective method of data analysis are presented. Correlations were sought between the occurrence of: lithium, potassium, rubidium, caesium, beryllium, strontium, barium, ammonium, amines, nitrate, nitrite, boron, mercury, sulfate, phosphate, fluorine, chlorine, bromine, iodine and carbon (both elemental and organic hydrocarbon) in both fine (d < 2.5 microm) and coarse (d > 2.5 microm) particle fractions. Several previously unreported correlations were observed, for instance between the elements lithium, beryllium and boron. The results suggest that about 2 in 3 of all fine particles (by number rather than by mass), and 1 in 2 of all coarse particles containing carbon, consisted of elemental carbon rather than organic hydrocarbon (although a bias in the sensitivity of the ATOFMS could have affected these numbers). The ratio of the number of coarse particles containing nitrate anions to the number of particles containing chloride anions exceeded unity when the air mass had travelled over the British mainland. The analysis also illustrates that an air mass of marine origin that had travelled slowly over agricultural land can accumulate amines and ammonium.     

Nutrient chemistry of River Pinios (Thessalia, Greece)

The impact of human activities with 3-year monitoring on the fluctuation of nutrients along the Pinios River and its tributaries were studied. Their seasonal variations throughout the years 1996-1998 were also presented. High temperatures, from June to August, cause a restriction of the water flow, an enhancement of nutrient concentration with the subsequent increase of eutrophication. High concentrations of nutrients were observed first in winter (wet period), caused by leaching of fertilizers from terrestrial systems after heavy rainfall, later during the warm months due to low water flow of the river, and at last in autumn when plant organisms began to decompose. The intensive algal and macrophyte growth (spring, summer) resulted in severe depletion of nutrients. Organic carbon showed no seasonal trend but its values were high near the estuaries. Nitrate fluxes were high at the initial station (sources) and the Titarisios tributary, whereas nitrites and ammonium were low. In contrary, the Kalentzis tributary with relatively low nitrate values showed increased values of nitrite ammonium or total nitrogen. On the other hand, the Enipeas tributary showed high SO4 values. Phosphates are remarkably present mainly after the city of Larissa, where sewage and industrial discharges occur. None of the nutrients measured in the Pinios River and its tributaries showed a clear seasonal cycle of concentration. Concentrations of nutrients and organic carbon increased as a consequence of anthropogenic inputs, particularly point discharges from sewage treatment plants (i.e. showing distinct, but variable, concentration peaks), as well as diffuse urban and/or agricultural runoff over long areas during storm events. The agricultural management, the urban pollution, mainly from Larissa City, and the climate conditions in the catchment basin (Thessalia Plain) of Pinios River and its tributaries greatly affect the chemical composition of their waters.     

Uranium series isotopes in the Avon Valley, Nova Scotia

An U-series isotopic study was carried out in the waters of the Avon Valley, Nova Scotia. The fresh and acidic recharge waters flow rapidly through the watershed composed of a granitic highland and a sedimentary, largely carbonate, lowland plain, before draining to the sea. There is no significant anthropogenic pollution; but, naturally elevated U levels can be encountered within the bedrock. Nonetheless, the U concentrations of the surface and groundwater are low (generally within the range of several hundredths to several tenths of a microg l(-1)), except in the proximity to weathering of U mineralization. The dissolved U in the surface waters appears to be stabilized by organic rather than inorganic complexes. Both the groundwaters and surface waters have similar (234)U/(238)U activity ratios that rarely deviate from secular equilibrium by more than 20% throughout the watershed. The magnitude of the (234)U/(238)U activity ratio is not determined by lithology but rather by the weathering mechanism, the high rate of flushing, and the leaching of local U mineralization. Dissolved Ra is consistently absent. The dissolved Rn concentrations, though variable, are measurable even in surface waters. This may be due to a continual degassing from the U-enriched bedrock or release from local sites of U mineralization underlying the surface water sources.     

90Sr migration to the geo-sphere from a waste burial in the Chernobyl exclusion zone

Results are presented from an ongoing field-scale experimental study (namely the Chernobyl Pilot Site project) aimed at characterization of processes controlling (90)Sr releases from a shallow trench containing nuclear fuel particles, and subsequent radionuclide transport in the underlying sandy aquifer at the Chernobyl nuclear power plant site. Microscopic analyses of waste material and leaching experiments have shown that 10-30% of the radioactive inventory is associated with chemically extra-stable Zr-U-O particles. The largest fraction of (90)Sr activity in the trench ( approximately 30-60%) is currently associated with relatively slowly dissolving non-oxidized UO(2) matrix fuel particles. The (90)Sr migration velocity in the eolian sand aquifer is retarded by sorption to approximately 9% of groundwater flow velocity (K(d) approximately 2 ml/g). The dispersivity values for non-reactive solute transport in the aquifer predicted by geostatistics (i.e. 0.8 6 cm) were confirmed by a natural gradient tracer test using (36)Cl. The observed negative correlation between hydraulic conductivity and K(d) of aquifer sediments suggests that (90)Sr could be subjected to larger dispersion in the subsurface compared with (36)Cl.     

An airborne gamma-ray spectrometry survey of nuclear sites in Belgium

As part of a wider study to define the existing background levels in Belgium an airborne gamma-ray survey was conducted in two areas associated with nuclear sites. In the Mol area, the survey zone included areas surrounding the SCK-CEN nuclear research centre, and its associated neighbourhood which includes radioactive waste stores, fuel manufacture and fabrication facilities and an international accelerator laboratory. In the vicinity of Fleurus, the survey included the IRE complex with radiochemical laboratories, irradiation facilities and stores, and isotope production accelerators. The survey was conducted using a twin engined helicopter equipped with a combined scintillation and semiconductor spectrometer. The system was installed and tested in the UK, and then transferred to Belgium for operations. The complete survey was conducted successfully within 1 week. The results provide a comprehensive record of the radiation environment of the nuclear sites at time of survey, and show a range of signals associated with the types of activity present in each area. They confirm that radiation fields are largely confined to the operational sites, and provide a traceable record against which future changes could be assessed. The demonstration of efficient deployment between two European countries, coupled with rapid mapping of many different radiometric signals around these sites confirms the utility of the airborne gamma spectrometry approach for accurate definition of enhanced radiation fields. This has important implications for emergency response.     

239+240Pu, 90Sr and 137Cs inventories in surface soils of Vietnam

Fallout 239+240Pu, 238Pu, 90Sr and 137Cs inventories in surface soils were measured for 20 locations in northern Vietnam yielding the mean values (+/- standard error) of 26.5+/-3.8 Bq m(-2) for 239+240Pu, 1048+/-143 Bq m(-2) for 137Cs and 212+/-28 Bq m(-2) for 90Sr. The concentrations of 137Cs and plutonium isotopes strongly correlate with each other resulting in a stable 239+240Pu/137Cs inventory ratio of 0.025+/-0.002. Among soil parameters, organic matter and fulvic acids strongly correlate with caesium and plutonium isotopes, especially in the 0-10 cm layer. 137Cs and 239+240Pu are distributed rather similarly over the 0-10 cm and 10-20 cm layers. At locations with high contents of sand (82-93%) along the South China Sea coast, the downward percolation by rainwater results in a higher accumulation of 239+240Pu and 137Cs in the 10-20 cm layer. The mean 137Cs/ 90Sr inventory ratio is 9.3+/-2.2, and the correlation is weak between these isotopes.     

Copper and zinc in four freshwater fish species from Lake Pamvotis (Greece)

Lake ecosystems are vulnerable to heavy-metal pollution. Fish samples are considered as one of the most indicative factors, in freshwater systems, for the estimation of trace metals pollution potential. Lake Pamvotis (NW Greece) is a typical Mediterranean ecosystem of great importance in regard to biodiversity and to aesthetic value. The fish species found most commonly in the lake are Cyprinus carpio, Silurus aristotelis, Rutilus ylikiensis, and Carassius gibelio. The aim of the present study is to evaluate the level of contamination of two essential heavy metals (copper and zinc) appearing at high concentrations in lake water in the above four fish species. Metal concentrations were measured by atomic absorption spectroscopy in three different tissues (muscle, liver, gonads) in order to assess the fish contamination. A two-factor analysis of variance, based on the procedure of general linear models, was employed in which fish species (four levels) and fish tissue (three levels) were examined for potential influence on Cu and Zn concentrations. Differences between level means per factor were treated using Tukey's multiple comparisons of means. The study showed that C. carpio and R. ylikiensis presented the highest metal content. Tissues analysis revealed that liver and gonads accumulated the highest levels of Cu and Zn. Metal concentration in the edible part of the examined fish (muscle) were in the safety-permissible levels for human consumption.     

Heavy metals in four fish species from the French coast of the Eastern English Channel and Southern Bight of the North Sea

Shallow coastal waters act as nurseries for various fish species and have been recognized as essential fish habitat. We studied heavy metal concentrations in four fish species (plaice, dab, flounder and cod) as an indicator of large-scale habitat quality. The study took place along the French coasts between the Eastern English Channel and the Southern Bight of the North Sea. All species show different concentrations of measured metals (e.g., Cd, Cu, Mn and Pb) in liver but not in muscle. The highest concentrations are found for the flounder and the lowest for cod which is consistent with their habitat and diet. Although our results do not highlight levels of appreciable pollution within the study area, inter-site differences are mainly observed in the muscle tissues and are generally in agreement with the known environmental data (e.g., anthropogenic pressure). However, in the Bay of Seine, one of the most contaminated estuaries in Europe, metal concentrations are in the same range or even lower than those found in fish collected from areas distant from any anthropogenic pressures. At one site, the comparisons of the Cd, Cu and Pb concentrations between healthy and diseased dabs have been carried out on the muscle and liver tissues. The results of this preliminary study show a relationship between metal concentrations and the pathological status of the fish. The use of fish health as indicator of habitat quality is discussed.