Accuracy and traceability in environmental monitoring--pitfalls in methylmercury determinations as a case study

The concepts of accuracy and traceability as applied to environmental analysis are still prone to misunderstandings. While accuracy refers to the closeness of analytical values to "true values" (trueness) and among various repetitions (precision), the term traceability implies a link of data obtained to established references through an unbroken chain of comparisons all with stated uncertainties. These misunderstandings, possibly occurring among the analytical community, may have consequences on environmental data interpretation. Recent discussions in the field of environmental speciation analysis illustrated that accuracy and traceability issues are still not firmly established within the environmental chemistry community. This paper discusses this issue, taking methylmercury as a case study.     

Organochlorine contaminants in seabird eggs from the Pacific coast of Canada, 1971–1986

Eggs were collected from seven seabird species at colonies on the British Columbia coast from 1983 to 1986 and analyzed for organochlorine contaminants. Total PCB levels (wet weight) were highest in double-crested cormorants (Phalacrocorax auritus) from the Fraser estuary (2.91 mg kg^-1) and the Strait of Georgia (3.79 mg kg^-1). Highest DDE levels were in fork-tailed storm-petrels (Oceanodroma furcata) from the Queen Charlotte Islands (1.68 mg kg^-1). Organochlorine levels were generally lower in eggs from the mid 1980s than in those collected in the early 1970s. Organochlorine levels in Pacific alcids and hydrobatids foraging in offshore locations were compared to those in the same or ecologically similar species from the Canadian Atlantic coast. DDT- and HCH-related compounds were higher in Pacific populations while levels of dieldrin, oxychlordane, and HCB were generally lower. With the exception of -HCH, levels of all measured organochlorines were lower in cormorants breeding in the Fraser River estuary than in cormorants from the St. Lawrence River estuary on the Atlantic coast.     

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.     

Water quality test based on dielectrophoretic measurements of fresh water algae Selenastrum capricornutum

A method is described whereby dielectrophoresis of algal cells is used to perform rapid water quality analysis, specifically detecting the presence of CuSO4. The dielectric collection spectrum of the fresh water alga Selenastrum capricornutum was determined for a range of concentrations of CuSO4 from 25 mg L(-1) to 0.25 mg L(-1) for exposure times of 15 min and 18 h. In all cases increasing the concentration of CuSO4 reduced cell collection, but a step reduction was observed in collection between 2 mg L(-1) and 5 mg L(-1). This method has potential for forming a rapid, low-cost test for water quality with broad specificity and significantly reduced analysis time compared to current methods.     

Determination of biomass burning emission factors: Methods and results

Biomass burning, in a broad sense, encompasses different burning practices, including open and confined burnings, and different types of vegetation. Emission factors of gaseous or particulate trace compounds are directly dependent both on the fuel type and the combustion process. Emission factors are generally calculated by stoichiometric considerations using the carbon mass balance method, applied either to combustion chamber experiments or to field experiments based on ground-level measurements or aircraft sampling in smoke plumes. There have been a number of experimental studies in the last 10 years to investigate wildfires in tropical, temperate, or boreal regions. This article presents an overview of measurement methods and experimental data on emission factors of reactive or radiatively active trace compounds, including trace gases and particles. It focuses on fires in tropical regions, that is, forest and savanna fires, agricultural burns, charcoal production, use of fuelwood, and charcoal combustion.     

Factor analysis of trace-element data from tree-bark samples in The Netherlands

Monte Carlo-assisted factor analysis has been applied to a data set of 20 trace-element concentrations in tree-bark samples obtained from 123 locations in The Netherlands, with the aim to investigate the suitability of bark as a biomonitor for air pollution. A Monte Carlo approach was used to give more insight to the uncertainties and significance levels of the factor analysis results. Notwith-standing a rather strong influence of soil material on the concentration levels, factor analysis enabled the identification of five significant pollution source types, all of which corresponded with source types found in an earlier biomonitoring study in The Netherlands using epiphytic lichens. A more detailed comparison with the lichen results showed a remarkable difference in lead concentrations between bark and lichen. It was concluded that bark can be successfully employed as a biomonitor for air pollution. The power of factor analysis to adequately determine the soil contribution may render extensive sample washing procedures superfluous.     

Characterizing soils for hazardous waste site assessments

This paper provides a review and justification of the minimum data needed to characterize soils for hazardous waste site assessments and to comply with the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA). Scientists and managers within the regulatory agency and the liable party need to know what are the important soil characteristics needed to make decisions about risk assessment, what areas need remediation and what remediation options are available. If all parties involved in characterizing a hazardous waste site can agree on the required soils data set prior to starting a site investigation, data can be collected in a more efficient and less costly manner. Having the proper data will aid in reaching decisions on how to address concerns at, and close-out, hazardous waste sites.This paper was prepared to address two specific concerns related to soil characterization for CERCLA remedial response. The first concern is the applicability of traditional soil classification methods to CERCLA soil characterization. The second is the identification of soil characterization data type required for CERCLA risk assessment and analysis of remedial alternatives. These concerns are related, in that the Data Quality Objective (DQO) process addresses both. The DQO process was developed in part to assist CERCLA decision-makers in identifying the data types, data quality, and data quantity required to support decisions that must be made during the remedial investigation/feasibility study (RI/FS) process. Data Quality Objectives for Remedial Response Activities: Development Process (US EPA, 1987a) is a guidebook on developing DQOs. This process as it relates to CERCLA soil characterization is discussed in the Data Quality Objective Section of this paper.     

Monitoring of the three organophosphate esters TBP,TCEP and TBEP in river water and ground water (Oder,Germany)

The behaviour of the three organophosphate esters tributyl phosphate (TBP), tris(2-chloroethyl)phosphate (TCEP) and tris(2-butoxyethyl)phosphate (TBEP) during infiltration of river water to ground water has been investigated. The monitoring site is the Oder River and the adjacent Oderbruch aquifer. From March 2000 to July 2001, 76 ground water samples from monitoring wells located close to the Oder River and nine river water samples were collected. Additionally, influent and effluent samples from local waste water treatment plants, one sample of rain water and samples of roof runoff were collected. All samples were analysed by solid-phase-extraction followed by gas chromatography/mass spectrometry. TBP, TCEP and TBEP were detected at mean values of 622 ng l(-1), 352 ng l(-1), and 2955 ng l(-1), respectively in municipal waste water effluents. This points to a major input of these compounds into the Oder River by municipal waste water discharge. The concentrations of TBP and TBEP decreased downstream the Oder River possibly due to aerobic degradation. TBP, TCEP and TBEP were detected in ground water influenced predominantly by bank-filtered water. This demonstrates a transport of organic compounds by river water infiltration to ground water. TBP, TCEP and TBEP were also detected in rain water precipitation, roof runoff and ground water predominantly influenced by rain water infiltration. This hints to an input of these compounds to ground water by dry and wet deposition after atmospheric transport. Organophosphate esters were also detected in parts of the aquifer at 21 m depth. This demonstrates low anaerobic degradation rates of TBP, TCEP and TBEP.