Development of an ombrotrophic peat bog (low ash) reference material for the determination of elemental concentrations

Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.     

Natural mercury enrichment in a minerogenic fen--evaluation of sources and processes

Mercury (Hg) records in natural archives such as peat bogs are often used to evaluate anthropogenic or climatic influences on atmospheric Hg deposition. In this context, there is an ongoing discussion about natural sources or processes of Hg enrichment in natural archives. In the present study we estimated Hg fluxes from rock weathering, direct atmospheric deposition and from indirect atmospheric deposition in the catchment of a pristine minerogenic fen (GC2) located in the Magellanic Moorlands, southernmost Chile. The Hg record in the bog covers 11 174 cal. (14)C years and shows Hg concentrations of up to 570 [micro sign]g kg(-1) with an average of 268 [micro sign]g kg(-1). Hg was found to be enriched in the peat by a factor of 81 if compared to the mean Hg concentrations in the rocks of the catchment (3.2 [micro sign]g kg(-1)). Hg and also Pb, Fe, and As were found to be enriched predominately in goethite layers indicating high retention of these elements in the bog by iron oxyhydrates. It could also be demonstrated that the high peat decomposition rates in minerogenic bogs can increase the Hg concentrations in the minerogenic peat by a factor of approximately 2 at the same atmospheric Hg deposition rate if compared to ombrotrophic sites. This study has shown that Hg in minerogenic peat can be naturally enriched especially through the retention by autochthonous formed goethite and can be a solely internal process which does not require increased external Hg fluxes.     

High frequency monitoring of the coastal marine environment using the MAREL buoy

The MAREL Iroise data buoy provides physico-chemical measurements acquired in surface marine water in continuous and autonomous mode. The water is pumped 1.5 m from below the surface through a sampling pipe and flows through the measuring cell located in the floating structure. Technological innovations implemented inside the measuring cell atop the buoy allow a continuous cleaning of the sensor, while injection of chloride ions into the circuit prevents biological fouling. Specific sensors for temperature, salinity, oxygen and fluorescence investigated in this paper have been evaluated to guarantee measurement precision over a 3 month period. A bi-directional link under Internet TCP-IP protocols is used for data, alarms and remote-control transmissions with the land-based data centre. Herein, we present a 29 month record for 4 parameters measured using a MAREL buoy moored in a coastal environment (Iroise Sea, Brest, France). The accuracy of the data provided by the buoy is assessed by comparison with measurements of sea water weekly sampled at the same site as part of SOMLIT (Service d'Observation du Milieu LIToral), the French network for monitoring of the coastal environment. Some particular events (impact of intensive fresh water discharges, dynamics of a fast phytoplankton bloom) are also presented, demonstrating the worth of monitoring a highly variable environment with a high frequency continuous reliable system.     

A comparison of X-ray fluorescence and wet chemical analysis of air filter samples from a scrap lead smelting operation

Personal and area air samples were taken at a scrap lead smelter operation in a bullet manufacturing facility. Samples were taken using the 37-mm styrene-acrylonitrile closed-face filter cassette (CFC, the current US standard device for lead sampling), the 37-mm GSP or "cone" sampler, the 25-mm Institute of Occupational Medicine (IOM) inhalable sampler, and the 25-mm Button sampler (developed at the University of Cincinnati). Polyvinylchloride filters were used for sampling. The filters were pre- and post-weighed, and analyzed for lead content using a field-portable X-ray fluorescence (XRF) analyzer. The filters were then extracted with dilute nitric acid in an ultrasonic extraction bath and the solutions were analyzed by inductively coupled plasma optical emission spectroscopy. The 25-mm filters were analyzed using a single XRF reading, while three readings on different parts of the filter were taken from the 37-mm filters. The single reading from the 25-mm filters was adjusted for the nominal area of the filter to obtain the mass loading, while the three readings from the 37-mm filters were inserted into two different algorithms for calculating the mass loadings, and the algorithms were compared. The IOM sampler was designed for material collected in the body of the sampler to be part of the collected sample as well as that on the filter. Therefore, the IOM sampler cassettes were rinsed separately to determine if wall-loss corrections were necessary. All four samplers gave very good correlations between the two analytical methods above the limit of detection of the XRF procedure. The limit of detection for the 25-mm filters (5 microg) was lower than for the 37-mm filters (10 microg). The percentage of XRF results that were within 25% of the corresponding ICP results was evaluated. In addition, the bias from linear regression was estimated. Linear regression for the Button sampler and the IOM sampler using single readings and the GSP using all tested techniques for total filter loading gave acceptable XRF readings at loadings equivalent to sampling at the OSHA 8-hour Action Level and Permissible Exposure Limit. However, the CFC only had acceptable results when the center reading corrected for filter area was used, which was surprising, and may be a result of a limited data set. In addition to linear regression, simple estimation of bias indicated reasonable agreements between XRF and ICP results for single XRF readings on the Button sampler filters, (82% of the individual results within criterion), and on the IOM sampler filters (77% or 61%--see text), and on the GSP sampler filters using the OSHA algorithm (78%). As a result of this pilot project, all three samplers were considered suitable for inclusion in further field research studies.     

The fate of fipronil in modular estuarine mesocosms

The degradation and corresponding product manifold for the pesticide fipronil was determined in three replicate estuarine mesocosms. Aqueous fipronil concentrations rapidly decreased over the 672 h timescale of the experiment (95% removal). Loss was apparently first-order in fipronil, although there appeared to be a change in the removal mechanism after 96 h that corresponded to a dramatic slowdown in its disappearance. The reduction product of fipronil, fipronil sulfide, was not detected in the water column; however, it formed rapidly in sediments and was identified as the major product of fipronil degradation in the system (20% yield at 672 h, with respect to initial fipronil concentration). Fipronil sulfone is thought to form primarily via biological oxidation; and, although it was generated rapidly in the water column (10% yield), only trace amounts were detected in the sediment (1% yield). The direct photolysis product of fipronil, fipronil desulfinyl, was present in all samples; it formed rapidly in the water column (4% yield) and partitioned into the sediment phase (7% yield) over the course of the experiment. The mass balance on fipronil and associated products was 42% at 672 h.     

How and why is Aquatic Quality Changing at Nahanni National Park Reserve, nwt, Canada?

Nahanni National Park Reserve is located at southwestern NWT-Yukon border. One of the first UNESCO World Heritage sites, Nahanni lies within Taiga Cordillera and Taiga Shield Ecozones. Base and precious metal mining occurred upstream of Nahanni prior to park establishment. Nahanni waters, sediments, fish, and caribou have naturally elevated metals levels. Baseline water, sediment and fish tissue quality data were collected and analyzed throughout Nahanni during 1988–91 and 1992–97. These two programs characterized how aquatic quality variables are naturally varying in space and time, affected by geology, stream flow, seasonality, and extreme meteorological and geological events. Possible anthropogenic causes of aquatic quality change were examined. Measured values were compared to existing Guidelines and site-specific objectives were established.     

A pilot project to detect and forecast harmful algal blooms in the northern Gulf of Mexico

More timely access to data and information on the initiation, evolution and effects of harmful algal blooms can reduce adverse impacts on valued natural resources and human health. To achieve this in the northern Gulf of Mexico, a pilot project was initiated to develop a user-driven, end-to-end (measurements to applications) observing system. A key strategy of the project is to coordinate existing state, federal and academic programs at an unprecedented level of collaboration and partnership. Resource managers charged with protection of public health and aquatic resources require immediate notice of algal events and a forecast of when, where and what adverse effects will likely occur. Further, managers require integrated analyses and interpretations, rather than raw data, to make effective decisions. Consequently, a functional observing system must collect and transform diverse measurements into usable forecasts. Data needed to support development of forecasts will include such properties as sea surface temperature, winds, currents and waves; precipitation and freshwater flows with related discharges of sediment and nutrients; salinity, dissolved oxygen, and chlorophyll concentrations (in vivo fluorescence); and remotely-sensed spatial images of sea surface chlorophyll concentrations. These data will be provided via a mixture of discrete and autonomous in situ sensing with near real-time data telemetry, and remote sensing from space (SeaWiFS), aircraft (hyperspectral imagery) or land (high-frequency radar). With calibration across these platforms, the project will ultimately provide a 4-dimensional visualization of harmful algae events in a time frame suitable to resource managers.     

Trihalomethanes in Drinking Water of Greater Québec Region (Canada): Occurrence, Variations and Modelling

The levels of trihalomethanes (THMs) – the main species of by-product from water chlorination – were monitored in thedistribution systems of the five major drinking water utilitiesof the greater area of Québec City in order to investigate andmodel their occurrence on a spatial and seasonal basis. Data forTHMs and other water quality and operational parametersassociated with their formation were generated through a 16 monthsampling program involving several sites representing variablewater residence times, from the plant to the system extremity.The results demonstrate that the differences in measured THMlevels between the five utilities are mainly due to the variablequality of raw waters, the type of water treatment process beingused and the type and levels of applied disinfectant. Dependingon the utility, average THM levels were from 1.3 to 2.5 timeshigher in the system extremities than in the water leaving thetreatment plant. Also, average levels of THMs measured in summerat the distribution system extremities were, depending on theutility, from 2.5 to 5 times higher than the average levelsmeasured in winter. The seasonal differences were found to besignificantly greater than those observed by others in waterutilities in the United States and Europe and are explained inlarge part by the considerable changes, over the year, in thequality and temperature of surface waters in Southern Québec. Forthe five utilities under study, multivariate regression modelswere developed in order to predict spatial and seasonalvariations of THMs. Both residual chlorine demand and temperaturewere found to be better, statistically, as predictors for THMoccurrence. The usefulness of the developed models for routineand long term water quality management, as well as for assessmentof human exposure to THMs, are also discussed.     

Benchmarking for best practice environmental management

Benchmarking of environmental performance to demonstrate theachievement of best practice environmental management is acomponent of a new form of licensing of industrialdischarges in Western Australia. The paper describes theapproaches to benchmarking for the critical environmentalissues for an alumina refinery and wastewater treatmentplant. It also describes the lessons learnt from thebenchmarking process on appropriate methods, the benefitsand difficulties in the benchmarking process, and changesthat would assist benchmarking for best practiceenvironmental management.