Suggested protocol for collecting, handling and preparing peat cores and peat samples for physical, chemical, mineralogical and isotopic analyses

For detailed reconstructions of atmospheric metal deposition using peat cores from bogs, a comprehensive protocol for working with peat cores is proposed. The first step is to locate and determine suitable sampling sites in accordance with the principal goal of the study, the period of time of interest and the precision required. Using the state of the art procedures and field equipment, peat cores are collected in such a way as to provide high quality records for paleoenvironmental study. Pertinent field observations gathered during the fieldwork are recorded in a field report. Cores are kept frozen at -18 degree C until they can be prepared in the laboratory. Frozen peat cores are precisely cut into 1 cm slices using a stainless steel band saw with stainless steel blades. The outside edges of each slice are removed using a titanium knife to avoid any possible contamination which might have occurred during the sampling and handling stage. Each slice is split, with one-half kept frozen for future studies (archived), and the other half further subdivided for physical, chemical, and mineralogical analyses. Physical parameters such as ash and water contents, the bulk density and the degree of decomposition of the peat are determined using established methods. A subsample is dried overnight at 105 degree C in a drying oven and milled in a centrifugal mill with titanium sieve. Prior to any expensive and time consuming chemical procedures and analyses, the resulting powdered samples, after manual homogenisation, are measured for more than twenty-two major and trace elements using non-destructive X-Ray fluorescence (XRF) methods. This approach provides lots of valuable geochemical data which documents the natural geochemical processes which occur in the peat profiles and their possible effect on the trace metal profiles. The development, evaluation and use of peat cores from bogs as archives of high-resolution records of atmospheric deposition of mineral dust and trace elements have led to the development of many analytical procedures which now permit the measurement of a wide range of elements in peat samples such as lead and lead isotope ratios, mercury, arsenic, antimony, silver, molybdenum, thorium, uranium, rare earth elements. Radiometric methods (the carbon bomb pulse of (14)C, (210)Pb and conventional (14)C dating) are combined to allow reliable age-depth models to be reconstructed for each peat profile.     

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.     

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.     

Trace Element Analyses in an Epiphytic Lichen and its Bark Substrate to Assess Suitability for Air Biomonitoring

Total concentrations of Cd, Cr, Fe, Ni, Pb and Zn were compared from October 1996 to April 1998 in Physcia biziana (Massal.) Zhalbr. v. leptophylla Vezda and in the bark of Quercus ilex L. sampled from the same trees at an urban park. Trace metal concentrations were also measured in the bark covered by the lichen thalli. The lichens showed significantly higher Cr, Fe, Ni and Zn concentrations than both uncovered and covered barks. By contrast, both types of barks had higher concentrations of Cd and Pb than lichens. Trace elements showed a wide temporal variation of concentrations both in the lichens and barks. No relationship was found between the analysed matrices as regards the time course of trace element concentrations.     

Dioxin-like compounds in pine needles around Tokyo Bay, Japan in 1999

Pine needle samples collected at ten spatially distant sites around Tokyo Bay in 1999 indicated a widespread lower troposphere pollution with ultra-trace dioxin-like compounds such as chlorodibenzo-p-dioxins (PCDDs), -furans (PCDFs), non-ortho- and mono-ortho-chlorobiphenyls (pPCBs), and -naphthalenes (PCNs). Elevated concentration of planar PCBs and the total PCNs were found at the sites which are located innermost to the Bay, suggesting the regional importance of the evaporative nature of the source of pollution by those compounds over this vast area. The concentrations and profiles for PCDDs and PCDFs remained largely uniform. An exception was the site near the town of Tateyama in the Chiba Prefecture, which is the southernmost but also relatively separate from the inner Bay. The site near Tateyama showed somehow background contamination with all compound groups and highly different profiles of PCNs. The principal component analysis (PCA) of the data matrix has revealed that around the Tokyo Bay, apart from the evaporative emission sources for PCNs and PCBs, combustion related processes also play an important role as sources of the ambient air contamination not only with PCDDs/Fs but also with chloronaphthalenes and planar chlorobiphenyls.     

A combination of micro-porous membrane liquid-gas extraction and solid-phase trapping for ultra trace determination of benzene in urine

A method was developed for the determination of benzene in urine. The sample was pumped through the donor channel of a membrane extraction unit with a micro-porous membrane, separating the donor channel from an identical acceptor channel purged with nitrogen. The analyte reached the acceptor channel by diffusion through the membrane and was then swept by the carrier to a solid sorbent tube, where it was trapped. The analyte was subsequently thermally desorbed and analyzed by gas chromatography (GC) with mass selective detection (MS). After optimization, the recovery was close to quantitative, or 95%. Purging the membrane unit with pure water in between the samples eliminated any memory effects. The linearity was good in the concentration range examined (20-4000 ng l(-1)), with a correlation coefficient of 0.9996. The repeatability at 50 ng l(-1) and 400 ng l(-1) was 1.4% and 1.2%, respectively. The limit of detection was 12 ng l(-1) and the limit of quantification 35 ng l(-1). This enables assessment of benzene exposures of occupationally exposed subjects, of smokers and the majority of the general population. The developed method can be easily automated.     

Water Quality Evaluation and Trend Analysis in Selected Watersheds of the Atlantic Region of Canada

Water quality indices (WQIs) have been developed to assess the suitability of water for a variety of uses. These indices reflect the status of water quality in lakes, streams, rivers, and reservoirs. The concept of WQIs is based on a comparison of the concentration of contaminants with the respective environmental standards. The number, frequency, and magnitude by which the environmental standards for specific variables are not met in a given time period are reflected in WQIs. Further, the water quality trend analysis predicts the behavior of the water quality parameters and overall water quality in the time domain. In this paper, the concept of WQI was applied to three selected watersheds of Atlantic region: the Mersey River, the Point Wolfe River, and the Dunk River sites. To have robust study, two different water quality indices are used: Canadian Water Quality Index (CWQI), and British Columbia Water Quality Index (BWQI). The complete study was conducted in two steps. The first step was to organize and process the data into a format compatible with WQI analysis. After processing the input data, the WQI was calculated. The second step outlined in the paper discusses detailed trend analysis using linear and quadratic models for all the three sites. As per the 25 years trend analysis, overall water quality for agriculture use observed an improving trend at all the three sites studied. Water quality for raw water used for drinking (prior to treatment) and aquatic uses has shown improving trend at Point Wolfe River. It is further observed that pH, SO₄, and NO₃ concentrations are improving at Dunk River, Mersey River, and Point Wolfe River sites. To ascertain the reliability and significance of the trend analysis, a detailed error analysis and parametric significance tests were also conducted It was observed that for most of the sites and water uses quadratic trend models were a better fit than the linear models.     

Photocatalytic degradation of phenol

In this study photocatalytic degradation of phenol in thepresence of UV irradiated TiO₂ catalyst andH₂O₂was investigated. Effects of TiO₂ andH₂O₂concentrations and pH on photocatalytic degradation were examined. The rate constants for photocatalytic degradation wereevaluated as a function of TiO₂ and H₂O₂ concentrations and pH of the solution. It was found thatphotodegradation is an effective method for the removal of phenoland disappearance of phenol obeyed first order kinetics. The amount of CO₂h produced during photocatalytic degradation wascorresponding to the complete mineralization. Photodegradationcan be an alternative method for the treatment of phenol containing wastewaters.     

The Chemistry of Soils, Rocks and Plant Bioindicators in Three Ecosystems of the Holy Cross Mountains, Poland

In June of 2000, biogeochemical study was carried out in three ecosystems of the Holy Cross Mountains (south-central Poland). This paper presents element concentrations and stable sulfur (and in one site lead) isotope ratios in rocks, detailed soil profiles, and plant bioindicators including epiphytic lichen Hypogymnia physodes (L.) Nyl., mosses (Pleurozium schreberi (Brid.) Mitt., Hypnum cupressiforme Hedw. S. Str., Hylocomium splendens (Hedw.) B.S.G.), Scots pine (Pinus sylvestris L.), common birch (Betula pendula Roth.), aspen (Populus tremula L.) and English oak (Quercus robur L.). Chemical analyses were performed with ICP-AES and AAS methods in the accredited laboratory (Central Chemical Laboratory of the Polish Geological Institute in Warsaw). The principal objective of this study was to compare the chemical composition of rocks, soils and selected plant bioindicators between investigation sites using the same methods of sample collection, preparation and analyses. The results of this study have shown that there is a high variability in concentrations of elements in plant bioindicators from the same sites that can not be explained only by soil properties or anthropogenic influence. This conclusion indicates that for biomonitoring purposes (especially with vascular plants) we cannot neglect individual features of the species examined.     

Application of a systemic approach to the study of pollution of the Tinto and Odiel rivers (Spain)

The province of Huelva in the SW of Spain presents high environmental contrasts: together with the great abundance of natural spaces, it shows the impacts of historical natural resources exploitation processes. In the Ria of Huelva, the effluents of the chemical industries must be added to the contaminating inputs of the Tinto and Odiel rivers, coming from the acid drainage of the mines located in the Iberian Pyrite Belt. This forced the Environmental Agency (AMA) to elaborate in 1987 an Effluent Remediation Plan in order to negate unacceptable environmental impacts. The application of a grey box systemic analysis to the AMD pollution, undergone by the Tinto and Odiel rivers has allowed to set a conclusive explanation of the sampling results observed for a period of 11 years, thus making available an overall view of the polluting process and, above all, an explanation of its partial aspects.