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).     

A study of the distribution of lead, cadmium and copper between water and kaolin, bentonite and a river sediment

Experiments were carried out to monitor the equilibrium distribution of lead, cadmium and copper between an aqueous phase modelling natural water and a solid phase modelling natural sediment, under varying conditions. The aqueous phase was analysed using ETAAS and differential pulse anodic stripping voltammetry (DPASV), whereas XRD and FTIR were used to study the solid phase. Sorption isotherms at constant pH were measured. Conditional distribution constants were calculated as functions of the pH, the time of equilibration and the amount of solid material. The results obtained stress the need for standardization of the approaches to the study of water-sediment interactions in order to be able to evaluate and compare the extensive data from field measurements and to predict these interactions.     

Insecticide Contamination of Jamaican Environment. V. Island-Wide Rapid Survey of Residues in Surface and Ground Water

Residues of organochlorines and organophosphates were determined by gas chromatography in water and sediment from 26 locations in 17 major rivers, 7 natural springs and 13 wells across Jamaica. Samples were collected on only one occasion between May and July, 1994. Residues of endosulfan were detected in all but three rivers; -endosulfan in 15 samples of sediment (0.9–108.1, mean = 28.93, S.E. = 7.198 g kg-1) and 13 of water (0.01–0.35, mean = 0.11, S.E. = 0.035 g L-1), -endosulfan in 5 sediment (15.29–49.35, mean = 30.56, S.E. = 7.132 g kg-1) and 12 water (0.05–0.31, mean = 0.14, S.E. = 0.031 g L-1) samples, and endosulfan sulphate in waters of three rivers (0.003–0.244 g L-1). Chlorpyrifos was present in 9 sediment (0.423-135.2, mean = 18.38, S.E. = 10.699 g kg-1) and two water (0.001–0.022 g L-1) samples, diazinon and ethoprophos in the sediment of one river each. Mean levels (g L-1) of and isomers and sulphate of endosulfan were 0.16 (S.E. = 0.057), 0.12 (S.E. = 0.036) and 0.15 (S.E. = 0.089), respectively, in four of the seven springs and 0.23 (S.E. = 0.052), 0.11 (S.E. = 0.029) and 0.26 (S.E. = 0.088), respectively, in seven of the thirteen wells monitored.     

A catalogue of urban hydrocarbons for the city of Leeds: atmospheric monitoring of volatile organic compounds by thermal desorption-gas chromatography

A method has been developed for the speciation and quantitative determination of hydrocarbons in urban air in the city of Leeds. Hydrocarbons were pre-concentrated by adsorbent tube air sampling and analyzed using thermal desorption and gas chromatography with flame ionization detection and structural confirmation by mass spectrometric detection. While automated volatile organic compound (VOC) analyzers produced data for a maximum of about 30 compounds simultaneously, with the method described here, a total of 68 C6-C12 hydrocarbons were measured simultaneously in one analysis at parts per billion (ppb) levels. Several monitoring surveys were performed, one during the winter of 1993 and the other in the summer of 1994, at a number of sites to investigate the levels of VOCs identified in the urban air of Leeds.     

Sampling Benthic Macroinvertebrates in a Large Flood-Plain River: Considerations of Study Design, Sample Size, and Cost

Estimation of benthic macroinvertebrate populations over large spatial scales is difficult due to the high variability in abundance and the cost of sample processing and taxonomic analysis. To determine a cost-effective, statistically powerful sample design, we conducted an exploratory study of the spatial variation of benthic macroinvertebrates in a 37 km reach of the Upper Mississippi River. We sampled benthos at 36 sites within each of two strata, contiguous backwater and channel border. Three standard ponar (525 cm²) grab samples were obtained at each site ('Original Design'). Analysis of variance and sampling cost of strata-wide estimates for abundance of Oligochaeta, Chironomidae, and total invertebrates showed that only one ponar sample per site ('Reduced Design') yielded essentially the same abundance estimates as the Original Design, while reducing the overall cost by 63%. A posteriori statistical power analysis ( = 0.05, = 0.20) on the Reduced Design estimated that at least 18 sites per stratum were needed to detect differences in mean abundance between contiguous backwater and channel border areas for Oligochaeta, Chironomidae, and total invertebrates. Statistical power was nearly identical for the three taxonomic groups. The abundances of several taxa of concern (e.g., Hexagenia mayflies and Musculium fingernail clams) were too spatially variable to estimate power with our method. Resampling simulations indicated that to achieve adequate sampling precision for Oligochaeta, at least 36 sample sites per stratum would be required, whereas a sampling precision of 0.2 would not be attained with any sample size for Hexagenia in channel border areas, or Chironomidae and Musculium in both strata given the variance structure of the original samples. Community-wide diversity indices (Brillouin and 1-Simpsons) increased as sample area per site increased. The backwater area had higher diversity than the channel border area. The number of sampling sites required to sample benthic macroinvertebrates during our sampling period depended on the study objective and ranged from 18 to more than 40 sites per stratum. No single sampling regime would efficiently and adequately sample all components of the macroinvertebrate community.     

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.     

Using Multiple Antibiotic Resistance and land use characteristics to determine sources of fecal coliform bacterial pollution

Multiple Antibiotic Resistance (MAR) analysis and regression modeling techniques were used to identify surface water areas impacted by fecal pollution from human sources, and to determine the effects of land use on fecal pollution in Murrells Inlet, a small, urbanized, high-salinity estuary located between Myrtle Beach and Georgetown, South Carolina. MAR analysis was performed to identify areas in the estuary that are impacted by human-source fecal pollution. Additionally, regression analysis was performed to determine if an association exists between land use and fecal coliform densities over the ten-year period from 1989 to 1998. Land-use variables were derived using Geographic Information System (GIS) techniques and were used in the regression analysis.MAR analyses were conducted by comparing the frequency and patterns of antibiotic resistance found in Escherichia coli isolates derived from surface water samples and from sewage sources in the Murrells Inlet sewage collection system. The MAR results suggest that the majority of the fecal pollution detected in the Murrells Inlet estuary may be from non-human sources, including fecal coliforms isolated from areas in close proximity to high densities of active septic tanks.A MAR Index, which measures the frequency of antibiotic resistance, was calculated for each of twenty-three water samples and nine sewage samples. The antibiotic resistance pattern comparisons were performed using cluster analysis. Although the MAR indices indicated that several surface water sites had potential human-source contamination, the cluster analysis suggests that only one sampling site had MAR patterns that were similar to those found in the sewage samples. This site was in close proximity to several large pleasure boats as well as a sewage collection system lift station, but was not near areas with active septic tanks. The results of the regression analysis also suggest that sewage sources and rainfall runoff from urbanized areas may contribute to fecal pollution in the estuary.     

Characterization of microbial communities from coastal waters using microarrays

Molecular methods, including DNA probes, were used to identify and enumerate pathogenic Vibrio species in the Chesapeake Bay; our data indicated that Vibrio vulnificus exhibits seasonal fluctuations in number. Our work included a characterization of total microbial communities from the Bay; development of microarrays that identify and quantify the diversity of those communities; and observation of temporal changes in those communities. To identify members of the microbial community, we amplified the 16S rDNA gene from community DNA isolated from a biofilm sample collected from the Chesapeake Bay in February, 2000. The resultant 75 sequences were 95% or more similar to 7 species including two recently described Shewanella species, baltica and frigidimarina, that have not been previously isolated from the Chesapeake. When the genera of bacteria from biofilm after culturing are compared to those detected by subcloning amplified 16S fragments from community DNA, the cultured sample exhibited a strong bias. In oysters collected in February, the most common bacteria were previously unknown. Based on our 16S findings, we are developing microarrays to detect these and other microbial species in these estuarine communities. The microarrays will detect each species using four distinct loci, with the multiple loci serving as an internal control. The accuracy of the microarray will be measured using sentinel species such as Aeromonas species, Escherichia coli, and Vibrio vulnificus. Using microarrays, it should be possible to determine the annual fluctuations of bacterial species (culturable and non-culturable, pathogenic and non-pathogenic). The data may be applied to understanding patterns of environmental change; assessing the health of the Bay; and evaluating the risk of human illness associated with exposure to and ingestion of water and shellfish.     

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.