Long Term Trends in Liver Neoplasm Epizootics of Brown Bullhead in the Black River, Ohio

Since 1980, liver neoplasms in brown bullhead and polynuclear aromatic hydrocarbons (PAH) in sediment have been researched in a series of studies on the Black River in Lorain, Ohio. In the early 1980s the liver cancer prevalence in fish of age 3 and older was high, ranging from 22% to 39% of the adult population. These high cancer rates corresponded to high levels of PAHs in the sediment resulting from long-term releases by an upstream coking facility (USX). In 1983 this coking plant was closed, and by 1987 the PAH in sediment had declined by about two orders of magnitude. Coincidentally the tumor prevalence in 1987 was only about one-fourth of that in the early 1980s. In 1990, the most contaminated sediments were dredged. Neoplasm surveys in 1992 and 1993 found liver tumor frequencies in mature bullhead were as high as or higher than in the early 1980s. However liver tumor incidence declined in 1994, especially among age 3 fish, where neoplasm incidence was zero. These age 3 fish were the first group sampled that were not present during the 1990 dredging. These data are consistent with a hypothesis that the increase in tumor prevalence in 1992 and 1993 was caused by exposure to buried PAH-contaminated sediments released by the dredging. This research points out the insight provided by long term effects studies.     

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).     

Human plasma levels of POPs,and diet among native people from Uelen,Chukotka

Some of the people living in the Chukotka Peninsula of Russia depend heavily on marine mammals, but little is known of the exact dietary patterns and plasma levels of POPs among these populations. In this study, POPs levels in plasma from 50 participants from the isolated community of Uelen (Bering Strait) were determined and related to dietary information obtained through a food frequency questionnaire. The intake of marine mammals was high and the combined intake of blubber from walrus, seal and whale was a significant predictor (p < 0.01) of plasma concentrations of sum PCBs and borderline for sum CDs (p = 0.02) and sum DDTs (p = 0.04). There was a significant gender difference in the levels of POPs, and among women there was a significant increase with age. Extensive breastfeeding and lower blubber intake among women could be possible explanations for this gender difference. Despite the high intake of blubber the plasma levels of PCBs and DDTs were lower than some of those reported for the East Coast of Greenland. The geometric mean values for sum PCBs (17 congeners) and sum DDTs were 1316 ng g(-1) lipids and 563 ng g(-1) lipids, respectively. PCB 163, which partly co-eluted with PCB 138, was found in high concentrations (40% of PCB 138). This raises questions regarding the validity of using PCB 138 and PCB 153 to calculate the level of Arochlor 1260. The geometric mean of sum CDs was 518 ng g(-1) lipids. Concentrations of beta-HCH (geometric mean; 410 ng g(-1) lipids) were higher than observed for other native populations depending on marine mammals. Transportation of beta-HCH by ocean currents through the Bering Strait into the Arctic Ocean or regional point sources might explain these elevated levels.     

Correlations in polycyclic aromatic hydrocarbon (PAH) concentrations in UK ambient air and implications for source apportionment

The extent of correlation in polycyclic aromatic hydrocarbon (PAH) concentration data obtained by the UK PAH Monitoring and Analysis Air Quality Network from March 2008 to November 2010 has been assessed. Application of principal component analysis (PCA) to the dataset has revealed that the concentrations of the vast majority of PAHs are very highly correlated. The use of diagnostic PAH ratios (including a new benzo[b]naph[2,1-d]thiophene/benzo[a]pyrene diagnostic ratio), and a novel 'combined diagnostic ratio - PCA' approach has revealed information about the main sources of PAH at individual Network sites, allowing the sites to be grouped in terms of those influenced by solid fuel use, industry and traffic, and those of an urban or rural nature. Solid fuel use has also been delineated from other fuel burning. Conclusions are drawn about a number of UK PAH Network sites - four sites are shown to be influenced significantly by solid fuel use, and the sites in South Wales and at London Marylebone Road are found to be located in distinct and unusual PAH pollution climates - the identification of a unique PAH pollution climate in South Wales is a key and novel conclusion of the work.     

Estimated Variability of National Atmospheric Deposition Program/Mercury Deposition Network Measurements Using Collocated Samplers

The National Atmospheric Deposition Program/Mercury Deposition Network (MDN) provides long-term, quality-assured records of mercury in wet deposition in the USA and Canada. Interpretation of spatial and temporal trends in the MDN data requires quantification of the variability of the MDN measurements. Variability is quantified for MDN data from collocated samplers at MDN sites in two states, one in Illinois and one in Washington. Median absolute differences in the collocated sampler data for total mercury concentration are approximately 11% of the median mercury concentration for all valid 1999–2004 MDN data. Median absolute differences are between 3.0% and 14% of the median MDN value for collector catch (sample volume) and between 6.0% and 15% of the median MDN value for mercury wet deposition. The overall measurement errors are sufficiently low to resolve between NADP/MDN measurements by ±2 ng·l⁻¹ and ±2 μg·m⁻²·year⁻¹, which are the contour intervals used to display the data on NADP isopleths maps for concentration and deposition, respectively.     

What do qualitative rapid assessment collections of macroinvertebrates represent? A comparison with extensive quantitative sampling

It is a fundamental tenet of Rapid Biological Assessments (RBA) that the samples collected reflect the community from which they are drawn. As with any biological sampling, RBA collections are subject to sampling error resulting in the omission of some taxa. The aim of this study is to compare the composition of RBA samples with an estimate of community structure based on extensive quantitative sampling. We used logistic regression to explore the relationships between the frequency of a taxon being collected in an RBA sample and its biological and ecological traits, namely its abundance, distribution, body size and habit. RBA samples and quantitative estimates of community structure were made in riffles in the Kangaroo and Nepean Rivers, New South Wales, Australia. Single RBA samples may collect up to 63% of the taxa that are collected by extensive quantitative sampling at a site. The frequency of a taxon being recorded in an RBA sample was significantly and positively related to all traits tested indicating a bias in the collection methods towards large, abundant and widely distributed taxa. Accordingly, taxa missed by RBA sampling were generally small, narrowly distributed or rare. These findings enhance our understanding of what RBA samples represent, and the bias and source of errors associated with RBA sampling. This study also quantifies the utility of RBA methods for biodiversity assessment.     

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.     

Metal Pollution Assessment of Sediment and Water in the River Hindon, India

The metal pollution in water and sediment of the River Hindon in western Uttar Pradesh (India) was assessed for Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn. The metal concentrations in water showed wide temporal variation compared with bed sediment because of variability in water discharge and variations in suspended solid loadings. Metal concentrations in bed sediments provided a better evaluation of the degree and the extent of contamination in the aquatic environment, Santagarh and Atali being the most polluted sites of the river. The ratio of heavy metals to conservative elements (Fe, Al, etc.) may reveal the geochemical imbalances due to the elevated metal concentrations normally attributed to anthropogenic sources. Metal/Al ratios for the bed sediments of the river Hindon were used to determine the relative mobility and general trend of relative mobility occurred Fe > Mn > Zn > Cr > Ni > Pb > Cu > Cd.