Excrement from Heron colonies for environmental assessment of toxic elements

Excrement cast from Great Blue Heron nests was collected during the nesting period of 1978 from four colonies in Washington and Idaho. Cheesecloth strips placed on the ground beneath the nests served as excrement collecting devices. Chemical analysis for lead, mercury and cadmium were performed on dried samples. Lead was the most abundant trace metal found in heron debris. The Idaho colony at Lake Chatcolet had an average concentration of 46 ppm in the beneath-nest samples and 6 ppm in control samples. A heron colony near Tacoma, Washington had beneath-nest samples averaging 28 ppm and control samples averaging 20 ppm. Two colonies located in the interior region of Washington had substantially lower concentrations of lead. The difference observed between colonies was attributed to their associations with a polluted watershed (Chatcolet colony) an interstate highway (Tacoma colony) and an unpopulated largely agricultural area (inland Washington).     

Strontium-90 in Canada goose eggshells and reed canary grass from the Columbia River,Washington

Strontium-90 (⁹⁰SR) released to the ground near the N Reactor at the U.S. Department of Energy's Hanford Site enters the Columbia River through shoreline seeps. The ⁹⁰Sr is then potentially available for uptake by plants and animals. The life history and foraging behavior of nesting Canada geese is such that female geese could ingest ⁹⁰Sr while foraging on shoreline plants. Radichemical analyses showed that goose eggshells taken from an island, downstream from the N Reactor, contained more ⁹⁰Sr than did eggshells collected from other downstream islands. Reed canary grass samples taken from shoreline areas immediately downstream from the N Reactor contained higher concentrations of ⁹⁰Sr than samples from other downstream areas. All goose eggshells did not contain enhanced levels of ⁹⁰Sr, and all reed canary grass samples did not contain enhanced levels of ⁹⁰Sr, but a relationship exists between the releases of ⁹⁰Sr to the Columbia River and the enhanced levels of ⁹⁰Sr in some of the environmental samples analyzed.Pacific Northwest Laboratory is operated by Battelle Memorial Institute for the U.S. Department of Energy under contract DE-ACO6-76RLO 1830.     

Survey of the occurrence of residues of methyl tertiary butyl ether (MTBE) in Dutch drinking water sources and drinking water

An indicative survey has been carried out in The Netherlands investigating the presence of methyl tertiary butyl ether (MTBE) in drinking water and the corresponding sources. In total, 71 different sites used for the preparation of drinking water in The Netherlands were sampled in two successive seasons in 2001 involving the analysis of 156 samples. (ground water (n = 88), surface water (n = 17), bank filtrate water (n = 6) and drinking water (n = 45)). To combine high sample throughput with high selectivity and sensitivity, off-line purge and trap for sampling and gas chromatography mass spectrometry equipped with an automated thermal desorption sampler (TDS-GC-MS) was selected as the preferred analytical methodology. The developed procedure enabled the analysis of at least 40 samples per day and provided a limit of quantification of 2 ng l(-1). In the first period 63 samples of raw water were analyzed. Concentrations ranged between < 10 ng l(-1) and 420 ng l(-1) with a median concentration below 10 ng l(-1). The second period was focused at the re-sampling of positive locations (MTBE > 10 ng l(-1)) and a few additional drinking water utilities of which both the raw and drinking water of the utilities were analyzed. The median concentration of MTBE in the selected set of drinking water samples was 20 ng l(-1) (n = 45). At one location MTBE was found at a level of 2900 ng l(-1) caused by point source contamination of the ground water (11 900 ng l(-1)). Special attention has been paid to the quality of the results by analyzing all samples in duplicate and the analysis of control samples during each series of analyses.     

Environmental monitoring of historical change in arsenic deposition with tree bark pockets

ICP-MS analysis recorded historical change (c. 1846 to 2002) in the arsenic concentration of bark included within the trunks (tree bark pockets) of two Japanese oak trees (Quercus crispula), collected at an elevated location approximately 10 km from the Ashio copper mine and smelter, Japan. The arsenic concentration of the bark pockets was 0.016 +/- 0.003 microg cm(-2) c. 1846 (n = 5) and rose 50-fold from c. 1875 to c. 1925, from approximately 0.01 to 0.5 microg cm(-2). The rise coincided with increased copper production in Ashio from local sulfide ores, from 46 tons per year in 1877 to 16,500 tons per year in 1929. Following a decline in arsenic concentration and copper production, in particular during the Second World War, a second peak was observed c. 1970, corresponding to high levels of production from both local (6,000 tons per year) and imported (30,000 tons per year) ores, smelted from 1954. Compared to the local ores, the contribution of arsenic from imported ores appeared relatively low. Arsenic concentrations declined from c. 1970 to the present following the closure of the mine in 1974 and smelter in 1989, recording 0.058 +/- 0.040 microg cm(-2) arsenic (n = 5) in surface bark collected in 2002. The coincident trends in arsenic concentration and copper production indicated that the bark pockets provided an effective record of historical change in atmospheric arsenic deposition.     

Integration of modeling,monitoring and laboratory observation to determine reasons for air quality violations

An attempt was made to explain ambient air quality violations in the vicinity of industrial plants. Micrometeorology, diffusion calculaations, ambient readings, and plant engineering data are all taken into consideration to ascertain whether the plant is or is not the principal offender.Scrutiny of hi-vol filters using scanning electron microscopy for particle size analysis and particle chemical make-up as an assessment technique is also described.Case histories using the above analytical techniques are discussed.Presented at the 16th National Conference on Energy and the Environment, May 23, 1979     

Ambient air concentrations of PCDDs,PCDFs, coplanar PCBs,and PAHs at the Mississippi Sandhill Crane National Wildlife Refuge,Jackson County,Mississippi

Our objective was to determine the levels of selected airborne contaminants in ambient air at the Mississippi Sandhill Crane National Wildlife Refuge, Mississippi, that might be affecting the health of endangered cranes living there. Two high-volume air samplers were operated at separate locations on the Refuge during May–September 1991. The sampling media were micro-quartz filters in combination with polyurethane foam plugs. Composite bimonthly samples from each station were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), coplanar polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). Overall, residue concentrations were low. The toxic PCDD isomer 2,3,7,8-tetra-CDD was not detected, nor was penta-CDD. There was no difference (P>0.05) in residue concentrations between stations or over time and meteorological parameters were not correlated with residue concentrations. Because contaminant levels and patterns may differ seasonally, we recommend that air samples collected during winter months also be analyzed for these same chemical groups.     

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).     

Monitoring of diazinon concentrations and loadings,and identification of geographic origins consequent to stormwater runoff from orchards in the Sacramento River watershed,U.S.A

Diazinon contamination of California's rivers has resulted in placing several rivers on the federal Clean Water Act § 303d list of impaired waterways. Impaired water body listing requiresthe development of Total Maximum Daily Loads (TMDL). Previous studies identified stormwater related diazinon pulses in California rivers. This study was conducted to monitor diazinonconcentrations in the Sacramento River watershed after rainfallevents, to ascertain whether pulses could be identified and, ifconcentrations of concern were observed, to estimate loadings anddetermine geographic origins of the insecticide. TMDL developmentrequires knowledge of contaminant sources, loadings, and geographic origins. Flow and diazinon concentrations peaked in the Sacramento River at Sacramento after the three largest stormsduring January and February 1994. Diazinon concentrations peakedconsequent to each of three storms. Diazinon concentrationsmeasured in the Sacramento River at Sacramento exceeded theCalifornia Department of Fish and Game acute and chroniccriteria for protection of aquatic life during January andFebruary for nine and nineteen days, respectively. Multipleexceedances were observed throughout the watershed. Diazinon loading and geographic origin differed with each of the three storms. The design of this study provides a useful template for others attempting to identify loadings and sources of contaminants in surface waters and to rectify aquatic ecosystemcontamination from various land use practices.     

Determining Ecoregions for Environmental and GMO Monitoring Networks

A representative environmental monitoring network at the regional scale cannot use raster-based or random sampling designs, but requires a stratified sampling procedure integrating different information layers, and it has to occur in ecologically differing homogeneous regions (ecoregions). These we have determined using a set of spatial strata with ecological variables which we analysed with classification and regression trees (CART). We present a framework for environmental monitoring, that covers different scales, and we transfer the framework to a potential GMO (genetically modified organisms) monitoring network. We use ecoregion and other environmental strata together with existing environmental monitoring networks to determine GMO monitoring sites more precisely.