Collaborative study to improve the quality control of rare earth element determinations in environmental matrices

In order to control the quality of rare earth determinations in environmental matrices, the Standards, Measurements and Testing Programme (formerly Community Bureau of Reference, BCR) of the European Commission has started a project, the final aim of which is to certify four types of matrices (tuna muscle, mussel tissue, aquatic plant and estuarine sediment) for their contents of a range of rare earth elements (Sc, Y and the lanthanides: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu). The elements U and Th were added to the study. The first part of this project consisted of an interlaboratory study which aimed to test the feasibility of preparation of environmental reference materials and to detect and remove most of the pitfalls observed in rare earth determinations. This paper presents the preparation of the four matrices for the intercomparison study and for the candidate reference material. The main results are presented of the interlaboratory study that was carried out prior to the certification campaign. This collaborative trial is the first attempt ever carried out at this scale to evaluate the state-of-the-art of rare earth determinations in the environment. Its impact on the improvement of chemical measurements will have positive effects on the comparability of data necessary for environmental monitoring.     

A Global Overview of Atmospheric Acid Deposition Fluxes

This paper presents a summary of globalacid deposition flux data taken from a globalassessment report on acid deposition prepared forUNEP/WMO (Whelpdale and Kaiser, 1996). There is a largevariation in the spacial coverage and reliability ofmonitoring around the world. Many more stationsmeasure wet deposition than collect appropriate datafor estimating dry deposition. The widespread regionswith highest precipitation concentrations anddeposition fluxes of sulphate and nitrate coincideclosely with the regions of highest density ofSO₂ and NO_x precursor emissions occurringprimarily in the mid-latitude, northern hemispherebelt where a large fraction of the worlds fossilfuels is consumed. Organic acids in precipitation makea minor contribution to acidity (<20%) inindustrial regions, but in the rest of the world theyare of same order, or even exceed, inorganic acids.Less is known about dry deposition, but it appears topredominate near strong emission sources with wetdeposition predominating farther downwind. The molarratio of the N/S contribution to acidic deposition isclose to 1.0 over large areas of Europe and NorthAmerica, but is highly variable elsewhere, beinghighest in equatorial regions due to biomass burningand lowest near smelters and other large sources of SO₂.     

Modeling of non-point source pollution in a Mediterranean drainage basin

SWAT ver. 2000 was used to predict hydrographs, and sediment, nitrate and total phosphorus loadings from a 1349 km² mountainous/agricultural watershed in Northern Greece. The model was calibrated and verified using continuous meteorological data from eight stations within the drainage area, and runoff, sediment and nutrient concentrations measured at nine stations located within the main tributaries of the watershed, for the time period from May 1st, 1998 to January 31st, 2000. Model validation methodology and resulting input parameters appropriate for Mediterranean drainage basins are presented. Predicted by the model hydrographs, sedimentographs and pollutographs are plotted against observed values and show good agreement. Model performance is evaluated using the root mean square error computation and scattergrams of predicted versus observed data. The validated model is also used to test the effectiveness of three alternative cropping scenarios in reducing nutrient loadings from the agricultural part of the watershed. The study showed that this model, if properly validated, can be used effectively in testing management scenarios in Mediterranean drainage basins.     

Chlorobiphenyl contaminants at Pladda and Garroch Head in the Firth of Clyde in relation to sewage sludge input

Sewage sludge dumped at Garroch Head in the Firth of Clyde contains significant quantities of chlorinated hydrocarbons, such as polychlorinated biphenyls (CBs). These compounds are lipophilic and resistant to degradation. They accumulate in the biota either from the water column or through the food chain, particularly in tissue with a high lipid content. Bottom dwelling fish, such as plaice, in the vicinity of the dump site will accumulate CBs from their environment. Eighteen of the 209 CBs were measured in plaice livers from the Garroch Head dump site and from Pladda, a site reasonably remote from the dump site but also in the Clyde, over a 7 year period prior to the cessation of dumping in December 1998. Concentrations of the congeners in the liver of fish caught at the dump site were, in general, higher than those in the liver of fish caught at Pladda. Concentrations in the plaice livers for the sum of 18 CBs ranged from 1611 to 8471 micrograms kg-1 lipid for Garroch Head samples and from 336.9 to 2635 micrograms kg-1 lipid for samples from Pladda. The data were evaluated using principal component analysis (PCA). Pattern analysis was undertaken by normalising to the recalcitrant CB 153. Livers from the dump site were found to have a higher proportion of the lower chlorinated CBs. CB patterns were similar at the Garroch Head dump site from year to year, but multivariate techniques showed that there were differences in pattern when normalised to CB 153.     

Study of the relationships between bone lead levels and its variation with time and the cumulative blood lead index, in a repeated bone lead survey

The study aims were to: (i) investigate long term human lead metabolism by measuring the change of lead concentration in the tibia and calcaneus; and (ii) assess whether improved industrial hygiene was resulting in a slow accumulation of lead in an exposed workforce. 109Cd excited K X-ray fluorescence was used to measure tibia lead and calcaneus lead concentrations in 101 workers in a secondary lead smelter. 51 subjects had had similar bone lead measurements 5 years previously. Most of the other subjects had been hired since the first survey. Measurements of whole blood lead were available for the large majority of subjects. Tibia lead concentrations fell significantly (p<0.001) in the 51 subjects with repeated bone lead measurements, from a mean of 39 microg Pb (g bone mineral)(-1) to 33 microg Pb (g bone mineral)(-1). The change correlated negatively with the initial tibia lead concentration, producing an estimate for an overall half-life of 15 years, with a 95% confidence interval of 9 to 55 years. Adding continuing lead exposure and recirculation of bone lead stores to the regression models produced half-life estimates of 12 and 9 years, respectively, for release of lead from the tibia. The repeat subjects showed no net change in calcaneus lead (64 microg Pb (g bone mineral)(-1) initially, 65 microg Pb (g bone mineral)(-1) 5 years later). Subjects not measured previously had average lead concentrations of 15 microg Pb (g bone mincral)(-1) in the tibia and 13 microg Pb (g bone mineral)(-1) in the calcaneus. The rate of clearance of lead from the tibia (9 to 15 years) is towards the more rapid end of previous estimates. The lack of a significant fall in the calcaneus lead was surprising. Attempts should be made to repeat this observation. If confirmed, it would have implications for models of lead metabolism. The relatively low lead concentrations in the non-repeat subjects are reassuring. However, observation after a longer period of employment would be desirable.     

Young northern pike,yellow perch and crayfish as bioindicators in a mercury contaminated watercourse

Young-of-the-year and yearling northern pike (Esox lucius), yearling yellow perch (Perca flavescens) and adult crayfish (Orconectes virilis) were collected in the mercury-contaminated Wabigoon/English/Winnipeg River System, Ontario, and analyzed for total mercury. Analysis of mercury concentrations in these organisms produced consistent geographical trends; i.e. mercury concentrations in biota downstream of Dryden > English River system > Winnipeg River system > control sites. In the Wabigoon River system the bioavailability of mercury increases with distance downstream of the historical point source. Mercury concentrations in the biota studied were highly correlated with mercury concentrations in fish species which are of sport and commercial interest. The locations where young fish obtain their bodyburdens are known typically within 100 m. The biota studied compare favourably with the criteria proposed by Phillips (1980) as prerequisites for biological indicators. The wide distribution of young pike, perch and crayfish in North America, Europe and Asia may enhance their appeal as biomonitors.The views expressed are those of the authors and do not necessarily reflect the views of the Ontario Ministry of the Environment. No endorsement should be inferred.     

Organochlorine contaminants in seabird eggs from the Pacific coast of Canada, 1971–1986

Eggs were collected from seven seabird species at colonies on the British Columbia coast from 1983 to 1986 and analyzed for organochlorine contaminants. Total PCB levels (wet weight) were highest in double-crested cormorants (Phalacrocorax auritus) from the Fraser estuary (2.91 mg kg^-1) and the Strait of Georgia (3.79 mg kg^-1). Highest DDE levels were in fork-tailed storm-petrels (Oceanodroma furcata) from the Queen Charlotte Islands (1.68 mg kg^-1). Organochlorine levels were generally lower in eggs from the mid 1980s than in those collected in the early 1970s. Organochlorine levels in Pacific alcids and hydrobatids foraging in offshore locations were compared to those in the same or ecologically similar species from the Canadian Atlantic coast. DDT- and HCH-related compounds were higher in Pacific populations while levels of dieldrin, oxychlordane, and HCB were generally lower. With the exception of -HCH, levels of all measured organochlorines were lower in cormorants breeding in the Fraser River estuary than in cormorants from the St. Lawrence River estuary on the Atlantic coast.     

Information needs for marine pollution studies

Information needed for the resolution of environmental problems is a commodity with an economic value. The minimum necessary information implies minimal costs. The formulation of the information is considered for the case of biocides that can disrupt marine ecosystems.     

Determination of biomass burning emission factors: Methods and results

Biomass burning, in a broad sense, encompasses different burning practices, including open and confined burnings, and different types of vegetation. Emission factors of gaseous or particulate trace compounds are directly dependent both on the fuel type and the combustion process. Emission factors are generally calculated by stoichiometric considerations using the carbon mass balance method, applied either to combustion chamber experiments or to field experiments based on ground-level measurements or aircraft sampling in smoke plumes. There have been a number of experimental studies in the last 10 years to investigate wildfires in tropical, temperate, or boreal regions. This article presents an overview of measurement methods and experimental data on emission factors of reactive or radiatively active trace compounds, including trace gases and particles. It focuses on fires in tropical regions, that is, forest and savanna fires, agricultural burns, charcoal production, use of fuelwood, and charcoal combustion.     

Ammonia uptake by plants

The paper considers the methodology and results of experimental determination of dry deposition and ammonia uptake by isolated plant leaves. Analytical expressions are proposed which allow a transition from rates obtained in an isolated chamber to dry ammonia deposition by standing crops leaves.