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.     

Assessing the Effects of Atmospheric Ethylene on Epinasty and Tuber Yield of Potato (Solanum Tuberosum L.) Near Polyethylene Manufacturing Plants

A multi-year programme was performed to assess the effects of atmospheric ethylene on potato (Solanum tuberosum L.) in the vicinity of polyethylene manufacturing plants. There was a strong temporal variation of the hourly ethylene concentrations measured close to the sources from 1982 through 1991. Growing seasonal means exceeded 12 g m^–3 ethylene, the threshold for phytotoxic effects under laboratory conditions. Young test plants of potato showed an epinastic response to enhanced levels of ethylene. This response was reversible and did not occur when atmospheric ethylene was not detected. Based on hourly observations for the growing seasons of 1984 through 1991, epinasty occurred on average during circa 5% of the growing season and varied from circa 1% in 1985 to circa 18% in 1991. At night, ethylene concentrations were higher and epinasty was more frequent than during daylight hours. The intermittent exposures to ethylene did not affect tuber yield for the growing seasons of 1982 through 1990. The occurrence of epinasty indicated that ethylene exposure levels in the vicinity of the industrial sources might be sufficiently high to affect sensitive plants.     

Multi-level screening of a proposed hazardous waste treatment and disposal facility site--a case study

A comprehensive environmental assessment (EA) is a pre-requisite before the site for developing a hazardous waste treatment and disposal facility (HWTDF) is selected. However, the resource limitations, especially for developing countries, often dictatethat the detailed EA be restricted to those sites, which are constraint free and have low hazard potentials. Thus, a preliminary screening exercise for assessing the suitability ofsite for developing the HWTDF needs to be carried out to avoid huge costs involved in detailed EA. While screening a HWTDF site,various factors such as present land use, ecologically sensitiveareas, geology and hydrogeology of the area, the quality and quantity of wastes, engineered safeguards, and the operationalprocedures that need to be adopted, are required to be addressed. In this paper, a multi-level screening criteria employing RemoteSensing, Constraint Mapping, Groundwater Pollution Potential Index (DRASTIC Index), and the Site Ranking was used to assess the suitability of a proposed site for the development of HWTDF.The study helped to identify various constraints at the proposedsite and their significance on the development of the HWTDF.     

Monitoring of Seasonal Vegetables for Pesticide Residues

Market samples (60) of six seasonal vegetables were monitoredduring 1996–1997 to determine the magnitude of pesticidalcontamination. The estimation of insecticide residuesrepresenting four major chemical groups i.e. organochlorine,organophosphorous, synthetic pyrethroid and carbamate, was doneby adopting a multiresidue analytical technique employingGC-ECD and GC-NPD systems with capillary columns. The testedsamples showed 100% contamination with low but measurableamounts of residues. Among the four chemical groups, theorganophosphates were dominant followed by organochlorines,synthetic pyrethroids and carbamates. About 23% of the samplesshowed contamination with organophosphorous compounds abovetheir respective MRL values. More extensive studies coveringdifferent regions of Haryana state are suggested to get a clearidea of the magnitude of vegetable contamination with pesticideresidues.     

The influence of metallurgy on the formation of welding aerosols

Recent research has indicated that insoluble ultrafine aerosols (ie., particles whose physical diameters are less than 100 nm) may cause adverse health effects due to their small size, and that toxicological response may be more appropriately represented by particle number or particle surface area. Unfortunately, current exposure criteria and the associated air-sampling techniques are primarily mass-based. Welding processes are high-temperature operations that generate substantial number concentrations of ultrafine aerosols. Welding aerosols are formed primarily through the nucleation of metal vapors followed by competing growth mechanisms such as coagulation and condensation. Experimental results and mathematical tools are presented to illustrate how welding metallurgy influences the chemical aspects and dynamic processes that initiate and evolve the resultant aerosol. This research suggests that a fundamental understanding of metallurgy and aerosol physics can be exploited to suppress the formation of undesirable chemical species as well as the amount of aerosol generated during a welding process.     

Identification of dredged sediment-derived soils in the alluvial plains of the Leie and the Upper and Sea Scheldt rivers (Belgium) based on physico-chemical soil properties

An approach was developed to identify surface soils affected by historical dredged sediment disposal in the alluvial plains of the Upper Scheldt, the Sea Scheldt and the Leie river. Dredged sediment-derived soils were identified based on field observations, comparative granulometric analyses and chemical analyses. Criteria developed were based on a comparison between reference data from 102 aerobic soil samples of areas known to be affected by dredged sediment disposal and 104 samples from undisturbed alluvial soils along the studied rivers. A comparative grain size analysis with optical laser diffractometry between the A and C horizon proved useful for the identification of levelled-up sites. The chemical soil characteristics that were most useful in identifying dredged sediment-derived soils were CaCO3, sulfur (S), organic carbon (OC) and phosphorus (P) contents, electrical conductivity (EC), and the C/P and C/S ratios. Criteria for concluding the origin of an investigated soil were specific for the studied area, but the approach presented may provide useful guidelines for developing criteria valid for different regions.     

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.     

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.