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).     

Using environmental stressor information to predict the ecological status of Maryland non-tidal streams as measured by biological indicators

In Maryland, U.S., an interim framework has recentlybeen developed for using biologically based thresholds, or `biocriteria', to assess the health of nontidal streams statewide at watershed scales. The evaluation of impairment is based on indices of biological integrity from the Maryland Biological Stream Survey (MBSS). We applied logistic regression to quantify how the biotic integrity of streams at a local scale is affected by cumulative effects resulting from catchment land uses, point sources, and nearby transmission line rights-of-way. Indicators for land use were developed from the remote sensing National Land Cover Data and applied at different scales. We determined that the risk of local impairment in nontidal streams rapidly increases with increased urban land use in the catchment area. The average likelihood of failing biocriteria doubled with every 10% points increment in urban land, thus an increase in urban land use from 0 to 20% quadruples the risk of impairment. For the basins evaluated in this study, catchments with more than 40–50% urban land use had greater than 80% probability of failing biocriteria, on average. Inclusion of rights-of-way and point sources in the model did not significantly improve the fit for this data set, most likely because of their low numbers. The overall results indicate that our predictive modeling approach can help pinpoint stream ecosystems experiencing or vulnerable to degradation.     

Biotreatability and kinetics of UASB reactor to mixtures of chlorophenol pollutants

In most natural ecosystems heterotrophic microorganisms encountercomplex mixtures of carbon sources, each of which is present at aconcentration of few micrograms per litre. This study examined the biotreatability and kinetics of an upflow anaerobic sludge blanket (UASB) reactor to complex mixtures of chlorophenols encountered in environmental conditions using on-line and off-line experimental studies. Results indicate that (1) steady-state concentration was quite lower (98.3 mg L^-1) with complex mixture of chlorophenols than steady-state concentration achieved when only 2.4 dichlorophenol (124 mg L^-1) was studied alone on the same reactor; (2) that toxiceffects of chlorophenols increase with increasing concentrationsof toxicant. (Onset of the inhibitory effect occurred at a lowerconcentration in multi-substrate than in single substrate utilization); (3) addition of alternative utilizable substrate can mitigate toxic effects and enhance degradation; (4) the relative concentration of substrate was critical in determiningutilization patterns. HPLC analysis of off-line experimental samples resulted in a steady-state treatment efficiency of68% for COD, 36% for 2-hlorophenol, 40.5% for 4-chlorophenol, 70.7% for 2,4-dichlorophenol, 53.2% for 2,4,6-trichlorophenol and 42% for pentachlorophenol in presence of glucose. Kinetic constant in terms of V _max and K _s were determined. K _s for the five chlorophenols ranged between 0.016 and 0.117 kg m^-3 day^-1 while V _max ranged between 0.056 and 0.244 kg m^-3 day^-1.     

Atrazine and Alachlor Inputs to Surface and Ground Waters in Irrigated Corn Cultivation Areas of Castilla-Leon Region, Spain

The inputs of atrazine and alachlor herbicides to surface and ground waters from irrigated areas dedicated to corn cultivation in the Castilla-León (C-L) region (Spain) as related to the application of both herbicides were studied. Enzyme-linked immunosorbent assays (ELISA) were used for monitoring the atrazine and alachlor concentrations in 98 water samples taken from these areas. Seventy-nine of the samples were of ground waters and 19 were of surface waters. The concentration ranges of the herbicides detected in the study period (October 1997–October 1998) were 0.04–25.3 g L^–1 in the surface waters and 0.04–3.45 g L^–1 in the ground waters for atrazine, and 0.06–31.9 g L^–1 in the surface waters and 0.05–4.85 g L^–1 in the ground waters in the case of alachlor. The highly significant correlation observed between the concentrations of both herbicides in the surface waters (r = 0.89, p < 0.001) pointed to a parallel transport of atrazine and alachlor to these waters. A study was made of the temporal evolution of the concentrations of both herbicides, and it was found a maximum recharge of atrazine in the ground waters for April 1998 and of alachlor in October 1997 and October 1998. The temporal evolution of the concentrations of both herbicides in surface waters was parallel. The highly significant correlations observed between atrazine concentrations determined by ELISA and by HPLC (r = 0.92, p < 0.001) and between alachlor concentrations also determined by both methods (r = 0.96, p < 0.001) confirmed the usefulness of ELISA for monitoring both herbicides in an elevated number of samples. Using HPLC, the presence in some waters of the alachlor ethanesulfonate (ESA) metabolite was found at a concentration range of 0.52–4.01 g L^–1. However the interference of ESA in the determination of alachlor by ELISA was negligible. The inputs of atrazine and alachlor to waters found in this study, especially the inputs to ground waters, could pose a risk for human health considering that some waters, though sporadically, are even used for human consumption.     

IMPACTS OF VISITORS ON SOIL AND VEGETATION OF THE RECREATIONAL AREA “NACIMIENTO DEL RÍO MUNDO” (CASTILLA-LA MANCHA, SPAIN)

This study examines the effects of recreational use on the soil and vegetation at a site of ecological importance (Nacimiento del Río Mundo, Albacete, Spain). The most visited sites showed increased soil compaction of approximately 50%, bare ground increase to 61 ± 10% and a decrease in richness (from 25 ± 2 to 15 ± 2 species), diversity (from 4.0 ± 0.1 to 2.7 ± 0.4) and stratification of plant species (from 80 ± 11 to 21 ± 4%). The most visited sites had 90% less plant species as compared to the least visited. Intense use was associated with the presence of nitrophilous plant and vegetal species with a morphology adapted to heavy trampling. The recreational areas showed a distribution pattern of impact radiating outwards from the most used and degraded point. At the most visited point, Los Chorros (the spring of the river), the impact radiated outwards for about 20 m. A pilot experiment examining the effects of one-year restriction to visitors for access to a formerly impacted area showed a plant cover increase by anthropic and not by native species of 57 percent units.     

Evaluation of interference to conventional and real-time PCR for detection and quantification of fungi in dust

Advances in polymerase chain reaction (PCR) have permitted accurate, rapid and quantitative identification of microorganisms in pure cultures regardless of viability or culturability. In this study, a simple sample processing method was investigated for rapid identification and quantification of fungal spores from dust samples using both conventional and real-time PCR. The proposed method was evaluated for susceptibility to interference from environmental dust samples. Stachybotrys chartarum and Aspergillus fumigatus were used as test organisms. The sensitivity of detection in pure culture was 0.1 spore DNA equivalents per PCR reaction corresponding to 20 spores ml(-1) in the sample. However, 1 spore DNA equivalent per PCR reaction corresponding to 200 spores ml(-1) in the sample was the lowest amount of spores tested without interference in dust samples spiked with spores of either fungal species. The extent of inhibition was calculated using conventional and real-time PCR reactions containing fungal spores, specific primers, specific probes (for real-time PCR) and various amounts of dust. The results indicate that the extent of inhibition by dust on PCR varies with the type and amount of dust, and number of spores. No interference in the analysis of spiked samples was detected from 0.2 mg ml(-1) of four real-life dust samples at p-value >0.05 using 2 x 10(4) spores for conventional PCR and 2 x 10(5) spores for real-time PCR. However, samples containing >0.2 mg ml(-1) real-life dust compromised the PCR assay. These results suggest the potential usefulness of a simple sample processing method in conjunction with PCR for monitoring the fungal content of aerosols collected from indoor environments.     

Pool of Dust Particles over the Asian Continent: Balloon-borne Optical Particle Counter and Ground-based Lidar Measurements at Dunhuang, China

Measurements of aerosols were made in 2001 and 2002 at Dunhuang (40 degrees 00'N, 94 degrees 30'E), China to understand the nature of atmospheric particles over the desert areas in the Asian continent. Balloon-borne measurements with an optical particle counter suggested that particle size and concentration had noticeable peaks in super micron size range not only in the boundary mixing layer but also in the free troposphere. Super-micron particle concentration largely decreased in the mid tropopause (from 5 to 10 km; above sea level, a.s.l.). Lidar measurements made during August 2002 at Dunhuang suggested the possibility that mixing of dust particles occurred from near the ground to about 6 km even under calm weather conditions, and a large depolarization ratio of particulate matter was found in the aerosol layer. The top of the aerosol layer was found at heights of nearly 6 km (a.s.l.). It is strongly suggested that nonspherical dust particles (Kosa particles) frequently diffused in the free atmosphere over the Taklamakan desert through small-scale turbulences and are possible sources of dust particles of weak Kosa events that have been identified in the free troposphere not only in spring but also in summer over Japanese archipelago. Electron microscopic experiments of the particles collected in the free troposphere confirmed that coarse and nonspherical particles observed by the mineral particle were major components of coarse mode (diameter larger than 1 microm) below about 5 km over Dunhuang, China.     

Assessment of Metal Contamination in Doñana National Park (Spain) using Crayfish (Procamburus Clarkii)

Water quality assessment in the Aznalcollar area was attempted using multivariate methods based on heavy metal concentrations in red swamp crayfish (Procamburus clarkii). Trace levels of four heavy metals, copper (Cu), zinc (Zn), cadmium (Cd) and lead (Pb), were detected in crayfish from eleven different stations. Principal component analysis (PCA) highlighted a gradient of contamination between the sampling stations. Cluster analysis (CA) distinguished three groups of stations. Discriminant analysis also differentiated three groups. The group centroids of the first discriminant function were used to devise an index that varies according to the source of the crayfish. These standardized values are proposed for use as a water quality index. The ability of this index to successfully predict environmental quality was proved with random samples.     

Total versus inhalable sampler comparison study for the determination of asphalt fume exposures within the road paving industry

Exposure to asphalt fumes has a threshold limit value (TLV of 0.5 mg m(-3) (benzene extractable inhalable particulate) as recommended by the American Conference of Governmental Industrial Hygienists (ACGIH). This reflects a recent change (2000) whereby two variables are different from the previous recommendation. First is a 10-fold reduction in quantity from 5 mg m(-3) to 0.5 mg m(-3). Secondly, the new TLV specifies the "inhalable" fraction as compared to what is presumed to be total particulate. To assess the impact of these changes, this study compares the differences between measurements of paving asphalt fume exposure in the field using an "inhalable" instrument versus the historically used 'total' sampler. Particle size is also examined to assist in the understanding of the aerodynamic collection differences as related to asphalt fumes and confounders. Results show that when exposures are limited to asphalt fumes, a 1:1 relationship exists between samplers, showing no statistically significant differences in benzene soluble matter (BSM). This means that for the asphalt fume ACGIH TLV, the 'total' 37-mm sampler is an equivalent method to the "inhalable" method, referred to as IOM (Institute of Occupational Medicine), and should be acceptable for use against the TLV. However, the study found that when confounders (dust or old asphalt millings) are present in the workplace, there can be significant differences between the two samplers' reported exposure. The ratio of IOM/Total was 1.37 for milling asphalt sites, 1.41 for asphalt paving over granular base, and 1.02 for asphalt over asphalt pavements.     

monitoring bioaccumulation of contaminants in the belted kingfisher (ceryle alcyon)

The belted kingfisher (Ceryle alcyon), acommon piscivore in the eastern United States, hasbecome a common endpoint in ecological riskassessments (ERA) because of their high consumptionof potentially contaminated aquatic prey. Whilebioaccumulation data and biosurveys may be used tosupport conclusions of ERAs for kingfishers, thereare currently no published data on contaminantconcentrations in kingfishers. Additionally,methods available for collecting biological samples(e.g., feathers, eggs, food debris, etc.) fromkingfisher burrows can be detrimental to thereproductive success of the birds. We present amethod for obtaining samples from burrows during orfollowing the nesting season. The method wasapplied to kingfisher burrows on the Oak RidgeReservation (ORR) in eastern Tennessee. Feathers,eggshells, and nestlings were collected from burrows and analyzed. In addition, carcasses ofthree adult kingfishers found dead on the ORR wereanalyzed. Metals and radionuclides were accumulatedby both juvenile and adult birds. Body burdens ofcadmium, lead, and cesium-137 in adult birds were belowlevels associated with toxicity. Concentrations of selenium and mercury were observed at potentiallytoxic levels. Contaminants in eggshells andnestling feathers indicate exposure, however, thereis insufficient information to evaluate thetoxicological significance of this contamination.National Laboratory Oak Ridge National Laboratory is managed for the U.S. Department of Energy by Lockheed Martin Energy Research Corp. under contract DE-AC05-96OR22464