Interlaboratory evaluation of endotoxin analyses in agricultural dusts--comparison of LAL assay and mass spectrometry

Endotoxin exposure is associated with wheeze and asthma morbidity, while early life exposure may reduce risk of allergy and asthma. Unfortunately, it is difficult to compare endotoxin results from different laboratories and environments. We undertook this study to determine if lipopolysaccharide (LPS) extraction efficiency could account for differences among laboratories. We generated and collected aerosols from chicken and swine barns, and corn processing. We randomly allocated side-by-side filter samples to five laboratories for Limulus assay of endotoxin. Lyophilized aliquots of filter extracts were analyzed for 3-hydroxy fatty acids (3-OHFAs) as a marker of LPS using gas chromatography-mass spectrometry. There were significant differences in endotoxin assay and GC-MS (LPS) results between laboratories for all dust types (p < 0.01). Patterns of differences between labs varied by dust type. Relationships between assay and GC/MS results also depended on dust type. The percentages of individual 3-OHFA chain lengths varied across labs (p < 0.0001) suggesting that each lab recovered a different fraction of the LPS available. The presence of large amounts of particle associated LPS and absence of a freezing thawing cycle were associated with lower correlations between LPS and bioactivity, consistent with an absence of Limulus response to cell-bound endotoxin. These data suggest that extraction methods affect endotoxin measurements. The LAL methods may be most suitable when comparing exposures within similar environments; GC-MS offers additional information helpful in optimizing sample treatment and extraction. GC-MS may be of use when comparing across heterogeneous environments and should be considered for inclusion in future studies of human health outcomes.     

Organic contaminants in the Firth of Clyde following the cessation of sewage sludge dumping

To assess contaminant concentrations in the Firth of Clyde in relation to the former sewage sludge dump site at Garroch Head, and investigate any temporal changes, fish have been sampled annually since 1992 and sediment since 1999. In addition, a further four locations in the Clyde (Holy Loch, Hunterston, Skelmorlie and Irvine Bay) have been sampled for fish and sediment since 1999. Chlorobiphenyls (CBs) were measured in fish samples and polycyclic aromatic hydrocarbons (PAHs) and CBs in sediment. Since sampling was initiated the concentration for the summation operatorICES7 CBs in fish liver has been consistently >500 microg kg(-1) lipid weight at Garroch Head and the other Clyde sites and lower at the reference sites (Pladda, Colonsay, Broad Bay). Although the lowest CB concentrations of the eleven year period in plaice liver from Garroch Head were found in 2002, CB concentrations were found not to have decreased significantly since sewage sludge dumping ceased in 1998. However, a change in CB profile was observed with fish liver collected between 1992 and 1998 from Garroch Head showing a lower proportion of the less chlorinated CBs compared to the 1999-2002 liver samples. Highest CB and PAH concentrations in sediment were found at Garroch Head and Holy Loch with concentrations at these sites being significantly higher than at all other sites.     

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.     

A framework for assessment and monitoring of arthropods in a lowland tropical forest

By applying principles of adaptive management, and by using the valuable information that arthropods provide from assessment and monitoring programs, managers can identify and reduce possible impacts on biodiversity in development projects. In 1996, the Smithsonian Institution's Monitoring and Assessment of Biodiversity program worked together with Shell Prospecting and Development Peru to establish an adaptive management program to protect biodiversity in a natural gas exploration project in a Peruvian rainforest. In this paper, we outlined the conceptual steps involved in establishing an assessment and monitoring program for arthropods, including setting objectives, evaluating the results and making decisions. We also present the results of the assessment using some of groups of arthropods, and summarize the steps taken to identify appropriate groups for monitoring.     

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.     

Current strategies in nitrite detection and their application to field analysis

The various analytical protocols that have been developed to aid the measurement of nitrite within environmental samples have been critically appraised and their applicability to field measurement assessed. The present communication presents a perspective on current techniques and technologies encompassing spectroscopic, electrochemical and chromatographic methodologies and highlights those that are liable to emerge in the near future. Commercial devices have been included and where appropriate the advantages and limitations posed by their operation within field contexts have been described.     

Should foliar cadmium concentrations be expressed on a dry weight or dry ash weight basis?

Foliar analysis is a valuable tool for evaluating the pollution status of forests. However, the use of foliar diagnosis in large-scale surveys is a complicated process owing to the high variability within the crown. The method used to express foliar concentrations has often been found to diminish the variability. The effect of the method used to express element concentrations on the spatial variability of cadmium (Cd) in the leaves of crack willow (Salix fragilis L.) was investigated by sampling the leaves of one willow at 292 locations in the crown, each sampling location having a volume of 0.027 m3 (0.3 m x 0.3 m x 0.3 m). Cadmium showed a distinct spatial trend in the crown of the tree. Concentrations as low as 2.4 mg kg(-1) dry weight (DW) or 23.1 mg kg(-1) dry ash weight (DAW) were obtained in the top of the crown, and 10.6 mg kg(-1) DW or 73.0 mg kg(-1) DAW in the bottom of the crown. The lower relative standard deviation and weaker correlation with the sampling height support the use of DAW in large-scale surveys especially. The lower variability of the DAW Cd concentration makes this variable less sensitive to fluctuations caused by differences in growing conditions and sampling methodology. However, the majority of publications in this field report metal concentrations on a DW basis. Therefore, the restrictions set on the use of results expressed on a DAW basis in large-scale surveys of foliar metal concentrations have to be offset against the advantages offered by a reduction of the variability in metal concentrations.     

Chromium speciation and fractionation in ground and surface waters in the vicinity of chromite ore processing residue disposal sites

Chromium concentrations of up to 91 mg l(-1) were found by ICP-OES for ground water from nine boreholes at four landfill sites in an area of S.E. Glasgow/S. Lanarkshire where high-lime chromite ore processing residue (COPR) from a local chemical works had been deposited from 1830 to 1968. Surface water concentrations of up to 6.7 mg l(-1) in a local tributary stream fell to 0.11 mg l(-1) in the River Clyde. Two independent techniques of complexation/colorimetry and speciated isotope dilution mass spectrometry (SIDMS) showed that Cr was predominantly (>90%) in hexavalent form (CrVI) as CrO4(2-), as anticipated at the high pH (7.5-12.5) of the sites. Some differences between the implied and directly determined concentrations of dissolved CrIII, however, appeared related to the total organic carbon (TOC) content. This was most significant for the ground water from one borehole that had the highest TOC concentration of 300 mg l(-1) and at which < 3% of Cr was in the form of CrVI. Subsequent ultrafiltration produced significant decreases in Cr concentration with decreasing size fractions, e.g. <0.45 microm, < 100 kDa, <30 kDa and < 1 kDa by the tangential-flow method. As this appeared related more to concentrations of humic substances than of TOC per se, horizontal bed gel electrophoresis of freeze-dried ultrafilter retentates was carried out to further characterise the CrIII-organic complex. This showed for the main Cr-containing fraction, 100 kDa-0.45 microm, that the Cr was associated with a dark brown band characteristic of organic (humic) matter. Comparison of gel electrophoresis and FTIR results for ultrafilter retentates of ground water from this borehole with those for a borehole at another site where CrVI predominated suggested the influence of carboxylate groups, both in reducing CrVI and in forming soluble CrIII-humic complexes. The implications of this for remediation strategies (especially those based on the addition of organic matter) designed to reduce highly mobile and carcinogenic Cr(VI)O4(2-) to the much less harmful CrIII as insoluble Cr(OH)3 are discussed.     

Preliminary air pollution monitoring in San Miguel, Buenos Aires

Passive diffusion samplers were employed in San Miguel(Buenos Aires Metropolitan Area) for a preliminary airpollution monitoring. The highest loads were observedin downtown, compared with an urban background site.Total suspended particulate matter (TSPM) varied from0.257 to 0.033 mg cm^-2 month^-1; dust was examinedfor particle nature and size distribution. A similartrend was observed for nitrogen dioxide (NO₂) andTSPM spatial distribution, suggesting that traffic isthe major pollution source. Sulphur dioxide (SO₂)values were low and rather homogeneous. Levels for theinvestigated pollutants are below EPA's guide linevalues. Geographic (flat area, near to Rio de LaPlata) and climatologic factors (rainfalls andvariable wind directions) contribute to disperse pollutants.     

Measurements of fractionated gaseous mercury concentrations over northwestern and central Europe, 1995-99

Although it makes up only a few per cent. of total gaseous mercury (TGM) in the atmosphere, the fraction of oxidised (divalent) mercury plays a major role in the biogeochemical cycle of mercury due to its high affinity for water and surfaces. Quantitative knowledge of this fraction present in mixing ratios in the parts-per-10(15) (ppq) range is currently very scarce. This work is based on approximately 220 data for divalent gaseous mercury (DGM) collected during 1995-99 in ambient air. Over the course of the measurements, the sampling and analytical methods were modified and improved. This is described here in detail and includes transition from wet leaching and reduction procedures to thermo-reductive desorption, the use of annular as well as tubular denuders and adoption of an automated sampling system. The concentration of DGM exhibited a strong seasonal behaviour in contrast to atomic gaseous mercury, with low values in winter and maximum values in summer. The DGM/TGM ratios were frequently found to be below the detection limit (< or = 1%) and in the range 1-5%. A trend of diurnal DGM patterns was observed and implies photolytically induced sources. Scavenging of DGM during rain events was also noticed.