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.     

Naphthalene and its biomarkers as measures of occupational exposure to polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAH) include compounds with two or more fused benzene rings, many of which are carcinogens. Industrial sources produce hundreds of PAH, notably in the coke- and aluminium-producing industries. Because PAH are distributed at varying levels between gaseous and particulate phases, exposure assessment has been problematic. Here, we recommend that occupational exposures to naphthalene be considered as a potential surrogate for occupational PAH exposure for three reasons. Naphthalene is usually the most abundant PAH in a given workplace; naphthalene is present almost entirely in the gaseous phase and is, therefore, easily measured; and naphthalene offers several useful biomarkers, including the urinary metabolites 1- and 2-hydroxynaphthalene. These biomarkers can be used to evaluate total-body exposure to PAH, in much the same way that 1-hydroxypyrene has been applied. Using data from published sources, we show that log-transformed airborne levels of naphthalene are highly correlated with those of total PAH (minus naphthalene) in several industries (creosote impregnation: Pearson r= 0.815, coke production: r= 0.917, iron foundry: r= 0.854, aluminium production: r= 0.933). Furthermore, the slopes of the log-log regressions are close to one indicating that naphthalene levels are proportional to those of total PAH in those industries. We also demonstrate that log-transformed urinary levels of the hydroxynaphthalenes are highly correlated with those of 1-hydroxypyrene among coke oven workers and controls (r= 0.857 and 0.876), again with slopes of log-log regressions close to one. These results support the conjecture that naphthalene is a useful metric for occupational PAH exposure. Since naphthalene has also been shown to be a respiratory carcinogen in several animal studies, it is also argued that naphthalene exposures should be monitored per se in industries with high levels of PAH.     

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.     

Analysis of BTEX and other substituted benzenes in water using headspace SPME-GC-FID: method validation

The analysis of BTEX and other substituted benzenes in water samples using solid phase microextraction (SPME) and quantification by gas chromatography with flame ionization detection (GC-FID) was validated. The best analytical conditions were obtained using PDMS/DVB/CAR fibre using headspace extraction (HS-SPME) at 50 [degree]C for 20 min without stirring. The linear range for each compound by HS-SPME with GC/FID was defined. The detection limits for these compounds obtained with PDMS/DVB/CAR fibre and GC/FID were: benzene (15 ng L(-1)), toluene (160 ng L(-1)), monochlorobenzene (54 ng L(-1)), ethylbenzene (32 ng L(-1)), m-xylene (56 ng L(-1)), p-xylene (69 ng L(-1)), styrene (35 ng L(-1)), o-xylene (42 ng L(-1)), m-dichlorobenzene (180 ng L(-1)), p-dichlorobenzene (230 ng L(-1)), o-dichlorobenzene (250 ng L(-1)) and trichlorobenzene (260 ng L(-1)). This headspace SPME-GC-FID method was compared with a previously validated method of analysis using closed-loop-stripping analysis (CLSA). The headspace SPME-GC-FID method is suitable for monitoring the production and distribution of potable water and was used, in field trials, for the analysis of samples from main intakes of water (surface or underground) and from the water supply system of a large area (Lisbon and neighbouring municipalities).     

Application of the benthic index of biotic integrity to environmental monitoring in Chesapeake Bay

The Chesapeake Bay benthic index of biotic integrity (B-IBI) was developed to assess benthic community health and environmental quality in Chesapeake Bay. The B-IBI provides Chesapeake Bay monitoring programs with a uniform tool with which to characterize bay-wide benthic community condition and assess the health of the Bay. A probability-based design permits unbiased annual estimates of areal degradation within the Chesapeake Bay and its tributaries with quantifiable precision. However, of greatest interest to managers is the identification of problem areas most in need of restoration. Here we apply the B-IBI to benthic data collected in the Bay since 1994 to assess benthic community degradation by Chesapeake Bay Program segment and water depth. We used a new B-IBI classification system that improves the reliability of the estimates of degradation. Estimates were produced for 67 Chesapeake Bay Program segments. Greatest degradation was found in areas that are known to experience hypoxia or show toxic contamination, such as the mesohaline portion of the Potomac River, the Patapsco River, and the Maryland mainstem. Logistic regression models revealed increased probability of degraded benthos with depth for the lower Potomac River, Patapsco River, Nanticoke River, lower York River, and the Maryland mainstem. Our assessment of degradation by segment and water depth provided greater resolution of relative condition than previously available, and helped define the extent of degradation in Chesapeake Bay.     

Production,respiration and net ecosystem metabolism in U.S. estuaries

Primary production, respiration, and net ecosystem metabolism (NEM) are useful indicators of ecosystem level trophic conditions within estuaries. In this study, dissolved oxygen data collected every half hour between January 1996 to December 1998 by the National Estuarine Research Reserve System Wide Monitoring Program were used to calculate primary production, respiration, and net ecosystem metabolism. Data from two sites at each of 14 Reserves were analyzed. On average, three quarters of the data available could be used to calculate metabolic rates. Data from two of the Reserves were used to evaluate the assumption of homogeneity of water masses moving past the oxygen sensor. Temperature was the single most important factor controlling metabolic rates at individual sites, although salinity was also important at about half the sites. On an annual basis, respiration exceeded gross primary production demonstrating that all but 4 of the 28 sites were heterotrophic.     

Competitive Retention of Lead and Cadmium on an Agricultural Soil

Lead and cadmium contamination of an agricultural soil has been studied using batch and column experiments. Thermodynamics of theretention phenomena may be represented by a Langmuir isotherm foran aqueous metal concentration up to 100 mg L^-1. First order kinetics with respect to the solid phase yield good predictabilityfor both batch and column experiments. Kinetics and thermodynamics of lead retention predominate over those ofcadmium. As a consequence, lead is preferentially retainedand can even displace sorbed cadmium. In the event of anspill involving both metals, cadmium would move further inthe soil and its aqueous concentration downstream could beeven higher than that of the influent solution, increasingpotential risks. A two-region model has been used to fit all the experimental results. Satisfactory predictions for column experiments are obtained with parameters which are consistent with those obtained for the batch experiments, for which sorption is described by a Langmuir isotherm including competitive retention.     

Bioindicator organisms: Heavy metal pollution evaluation in the Ionian Sea (Mediterranean Sea—Italy)

Trace metal concentrations of mercury, cadmium, lead and chromium in Patella caerulea, and Mullus barbatus were investigated to provide information on pollution of Ionian Sea, since these metals have the highest toxic potential. High chromium levels (0.47–0.97 g g^–1 ww) were registered in limpet samples collected from two station near the Gulf of Taranto, while elevated concentration of mercury (0.31–1.50 g g^–1 ww) were found in mullet specimens from Sicily. The metal concentrations recorded at the clean stations may be considered as useful background levels to which to refer for comparison within the Mediterranean area. On the contrary, the high levels of chromium and mercury found respectively in the areas near the Gulf of Taranto and at Capo Passero being of concern in terms of environmental health need frequent monitoring.