Influence of environmental parameters on the accuracy of nitrogen dioxide passive diffusion tubes for ambient measurement

Two studies at three sites in the UK provided confirmation that systematic positive bias in NO2 diffusion tube measurement occurred because of changes to "within-tube" chemistry, rather than eddy diffusion at the mouth of the tube. In the first study in Cambridge, UK, sampler overestimation for 1 and 2 week exposures was compared to corresponding time-averaged monitor measurements (NO-NO2-NOx, O3) and weather variables. Noninearity between sampler and monitor NO2 measurements was interpreted in terms of spatial and temporal variations in relative and absolute availability of NO, NO2 and O3 at the site. A maximum overestimation occurred for an exposure mean NO2/NOx approximately 0.5. The separate contributions of reduced NO2 photolysis and eddy diffusion were compared in Study II using samplers of two materials, acrylic and quartz, and of different lengths (40, 55, 71 and 120 mm) at three sites: Norwich background, Cambridge intermediate, London kerbside. For compared sites, NO2 measured by acrylic samplers was significantly higher than for equivalent quartz samplers. For quartz samplers [NO2]mean was only just above the monitor at Norwich and London; sampler/monitor NO2 = 1.04 (P = 0.59) and 1.01(P = 0.76), respectively. For acrylic samplers the order of [NO2]mean was 40 mm > 120 mm > 71 mm > or = 55 mm. Excepting 40 mm samplers, this accords with a chemical bias where co-diffusing NO and 03 molecules in longer tubes have more time to react to form excess NO2. Bias in 40 mm samplers is discussed. Eddy diffusion is negligible for standard samplers because [NO2]mean was equivalent for 55 mm and 71 mm acrylic samplers and close to monitor NO2 for 71 mm quartz tubes. Both studies showed that sampler accuracy was dependent on location. Significantly, overestimation was greatest (approximately 3-4 ppb) where the NO2 annual mean was approximately 20 ppb, close to the UK and EU air quality standard of 21 ppb.     

Forest Area in Costa Rica: A Comparative Study of Tropical Forest Cover Estimates over Time

Forest area figures, at a given point in time and for a given region of interest, differ considerably, affecting the calculation of deforestation rates and thus confuse the political and scientific discussion on the state and change of the resource forest. This article discusses the variation of published forest cover figures, using Costa Rica as an example. A list of published figures on the forest cover of Costa Rica from 1940 onwards is analyzed. Reasons for the differences are hypothesized and discussed. These differences are mainly in the definition of forest and forest classes included, in the type of the studies conducted (mapping and/or sampling), in the precision of the estimates, and in the information sources used. It is concluded that part of the problem is inherent in the nature of the resource `forest'. Quality and completeness of the presentation of the forest cover estimates are a clue to their correct understanding and interpretation. The latter point being especially relevant, as forest cover data have both a technical-scientific and a political meaning and are used as relevant arguments in many discussions. In the example of Costa Rica, a general downward trend is observed up to about 1985/1990, whereas after that forest area figures are on the average at a markedly higher level. Some hypotheses for this change in the trend are discussed.     

Seasonal variations in nickel and vanadium in Mont Blanc snow and ice dated from the 1960s and 1990s

Ni and V have been determined in snow and ice collected at a high altitude location (Col du D?me) near the summit of Mont Blanc on the French-Italian border; dated from the 1960s and 1990s. Ni and V were simultaneously determined by inductively coupled plasma sector field mass spectrometry. Measured concentrations range from 6 to 700 pg g(-1) and 4 to 1,100 pg g(-1) for Ni and V, respectively. The results show pronounced seasonal variations in the concentrations of both metals, with high concentration values in summer layers and much lower values for winter layers. These seasonal variations are linked especially with the existence of inversion layers during winter months. Ni and V concentrations in excess of the contributions from rock and soil dust (Ni(excess), V(excess)) appear to be mainly associated with anthropogenic inputs, with pronounced seasonal variations. Large variations in the V(excess)/Ni(excess) ratio are observed, with a higher ratio in summer than in winter. This shows differences in anthropogenic inputs at Col du D?me during the different parts of the year. The above ratio was compared with the corresponding ratios for oil combustion from stationary sources and the exhaust from gasoline and diesel engines. It appears that Ni and V concentrations at Col du D?me are probably the result of changing combinations of contributions from oil combustion for power generation, industrial and residential uses, on one side, and automobile and truck traffic, on the other side, with possibly a significant contribution from Ni smelters in Russia during winter months.     

Pollen allergy related to the area of residence in the city of Córdoba,south-west Spain

The aim of this study was to analyse the relationship between the distribution of hay-fever patients in the city of Córdoba, south-western Iberian Peninsula, and the specific atmospheric biological content originating from local sources. Four different districts were established in the metropolitan area of the city, according to vegetational and urbanistic characteristics. Air samples were taken in each area using portable Hirst-type samplers (Lanzoni VPPS 1000) and the spectrum of biological content was defined. Patients attending the Allergy Unit at Córdoba Teaching Hospital in 2000 with allergic rhinitis and/or asthma, and displaying a positive reaction to aeroallergen extracts, were distributed within the areas as a function of their district of residence. Aerobiological results revealed differences in pollen content between areas, in terms of both quantity and number of pollen types recorded. These differences were largely due to proximity to rural areas, prevalence of pollen from typically urban species and the possible effect of urban architecture as a barrier to the dispersal/ concentration of particles and other pollutants. Patients were not uniformly distributed within the city. The majority lived in districts in which pollen from rural species was mixed with pollen from ornamentals. Patients living in typically urban districts displayed a higher prevalence of allergy to pollen from ornamentals. It is concluded that a high degree of exposure to the same environment may influence the development of sensitisation to the particular pollen load associated with that area.     

A ten channel fibre-optic device for distributed sensing of underground hydrocarbon leakage

With millions of fuel storage tanks and oil pipelines installed around the world, there is inevitably frequent leakage of potentially hazardous hydrocarbons. As many of these installations are below ground, it can often be many years before the extent of the leak is discovered. We have previously reported the development of a sensor for the detection of such subterranean leaks, using infrared reflectometry to interrogate a hydrocarbon sensitive membrane. However, a single sensor cannot provide any information about the flow rate or direction of the leak. This paper describes the extension of the technology to a multi-channel distributed sensing system, using optical fibres capable of distributing the sensors over large subterranean areas. Results are reported from the evaluation of the device, which consisted of monitoring the movement of different hydrocarbons (gasoline, diesel and insulating oil) through a vertical sand-filled vessel.     

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.     

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.     

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).     

Monochlorobenzene Marine Risk Assessment with Special Reference to the Osparcom Region: North Sea

This risk assessment on monochlorobenzene was carried out for the marine environment, following methodology given in the EU risk assessment Regulation (1488/94) and Guidance Document of the EU New and Existing Substances Regulation (TGD, 1996). Data from analytical monitoring programmes in large rivers and estuaries in the North Sea area were collected and evaluated for effects and environmental concentrations. Risk is indicated by the ratio of predicted environmental concentration (PEC) to predicted no-effect concentration (PNEC) for the marine aquatic environment. In total, 27 data for fish, 24 data for invertebrates and 13 data for algae were evaluated. Acute and chronic toxicity studies were taken into account and appropriate assessment factors used to define a final PNEC value of 32 micro/l. Recent monitoring data indicate that monochlorobenzene levels in surface waters are below determination limits of 0.1, 0.2, 0.5 microg/l used in monitoring programs. Assuming that half of the lowest determination (0.1 microg/l) is typical, a PEC of 0.05 microg/l was derived. A worst case of 0.5 microg/l is assumed. PEC/PNEC ratios give safety factors of 60 to over 500, taking no account of dilution in the sea. Monochlorobenzene is not a 'toxic, persistent and liable to bioaccumulate' substance sensu the Oslo and Paris Conventions for the Prevention of Marine Pollution (OSPAR-DYNAMEC) criteria. Environmental fate and effects data indicate that current use of monochlorobenzene poses no unacceptable risk to the aquatic environment.     

Polycyclic aromatic compounds in Northwest Atlantic COD (Gadus morhua)

Twenty-seven polycyclic aromatic compounds (PAC) including polycyclic aromatic hydrocarbons (PAH) and polycyclic aromatic sulphur heterocycles were analysed in muscle, liver and ovaries of cod (Gadus morhua) from the Northwest Atlantic. These PAC include the 16 PAH priority pollutants (EPA recommendation), alkylated naphthalenes, phenanthrene-anthracenes as well as dibenzothiophenes (DBT). Aromatics were undetectable in muscle. One of the analysed PAC was detected in one ovary and six in another ovary sample. Liver samples contained between 1 and 9 PAC. Of the parental PAH, only acenapthene (18 ng/g, dry weight), fluorene (28 ng/g) and chrysene (22 ng/g) were detected once each in two liver samples, while fluorene (72 ng/g) was detected once in one of the ovaries. C-2 DBT was the major component in ovaries and liver (8-86 ng/g), while C-3 and C-4 alkylated phenanthrene-anthracene (12-78 ng/g) were the next major components detected in the liver samples. This is the first detailed study of PAH and PAC in finfish from the Northwest Atlantic.