From radiometry to chronology of a marine sediment core: A 210Pb dating interlaboratory comparison exercise organised by the IAEA.

Laboratories from 14 countries (with different levels of expertise in radionuclide measurements and 210Pb dating) participated in an interlaboratory comparison exercise (ILC) related to the application of 210Pb sediment dating technique within the framework of the IAEA Coordinated Research Project. The laboratories were provided with samples from a composite sediment core and were required to provide massic activities of several radionuclides and an age versus depth model from the obtained results, using the most suitable 210Pb dating model. Massic concentrations of Zn and Cu were also determined to be used for chronology validation. The ILC results indicated good analytical performances while the dating results didn't demonstrate the same degree of competence in part due to the different experience in dating of the participant laboratories. The ILC exercise enabled evaluation of the difficulties faced by laboratories implementing 210Pb dating methods and identified some limitations in providing reliable chronologies.

PCBs occurrence in marine bivalves and fish from Todos os Santos Bay, Bahia, Brazil.

In order to evaluate contamination by polychlorinated biphenyls (PCBs) in a tropical bay exposed to different anthropogenic pressures, samples of bivalves: mangrove oyster (Crassotrea rhizophorae), mangrove mussel (Mytella guyanensis)and clams (Anomalocardia brasiliana), were collected in different parts of Todos os Santos Bay, Bahia, Brazil. In addition, samples of bivalves and fish, purchased from a seafood market in the city of Salvador were analyzed to evaluate human exposure to PCBs through ingestion. Identification and quantification of PCBs were done by GC/MS after microwave extraction and purification with sulfuric acid. In bivalves, concentrations ranged from <0.08 to 50.1 ng g -1 (dry weight), with the highest values being detected in mangrove oyster, followed by clams and mangrove mussel of the Subaé estuary and Madre de Deus/Mataripe; regions known to be impacted by anthropic activities. From the total of the 12 fish species analyzed, only 5 presented levels of PCBs above the detection limit, ranging from 0.23 to 4.55 ng g -1 and 0.51 to 26.05 ng g -1 by dry weight and lipid weight, respectively. In general, concentrations of PCBs on the bay are lower than in most regions around the world, especially those located in the Northern Hemisphere. Indexes indicated that local biota and seafood from the fish market are not adversely impacted by PCBs and do not represent a risk to human health.

Historical records of mercury deposition in dated sediment cores reveal the impacts of the legacy and present-day human activities in Todos os Santos Bay, Northeast Brazil.

We determined depth profiles of total mercury (T-Hg) in six 210Pb-dated sediment cores from Todos os Santos Bay to reconstruct the history of anthropogenic Hg accumulation. We also assessed superficial sediments samples from five estuaries. T-Hg concentrations (5-3500 µg kg-1) presented a large spatial and temporal variability. T-Hg concentrations in Ribeira Bay increased up to 200-fold along time, whereas the fluxes of T-Hg are substantially higher (up to 10,000 fold) than present-day wet deposition for industrialized areas. Sedimentary records indicate that a chlor-alkali plant has been the main source of Hg pollution until the present, although the T-Hg records suggest that harbor, shrimp farming, and oil refinery activities, besides Hg atmospheric depositions, are important across the bay. Sediments in the Ribeira Bay act as an important Hg sink. If sediments are eroded or disturbed, they may release Hg, thus posing a serious risk to wildlife and ecosystem health. CAPSULE: Sedimentary cores provide data on preindustrial levels and also anthropogenic fluxes of Hg for the appraisal of the magnitude, processes and potential risks of the contamination.

Chronology of anthropogenic impacts reconstructed from sediment records of trace metals and Pb isotopes in Todos os Santos Bay (NE Brazil).

The evolution of the impacts of anthropogenic activities in Todos os Santos Bay was evaluated by profiles of trace metals and Pb isotopes determined in sediment cores. Fluxes of metals increased up to 12, 4 and 2 times for Cu, Pb, and Zn, respectively, compared to those recorded in the beginning of the 20th century. Stable Pb isotopes identified a decommissioned lead smelter and burning of fossil fuels as the main sources of Pb. Most metals showed minor to moderate enrichment factors (EF<4), but Cu and Pb were highly enriched (EF=28 and 6, respectively) at the Aratu harbor. Temporal changes in sediments were associated to different activities, namely Pb smelting, burning of fossil fuels, maritime traffic, petroleum related activities, inputs of domestic effluents, and changes in land uses. The effects of the implementation of environmental policies to improve the waters of the bay could not be identified in the evaluated cores.

A tropical bay as a reference area defined by multiple lines of evidences.

References areas are sites that have undergone little or no anthropogenic impact and therefore represent the natural state of an environment. The objective of this study was to test if the Camamu Bay (CB), Bahia, can be used as a reference area for tropical coastal environments. Trace and major elements, polycyclic aromatic hydrocarbons (PAH), and the structure of the benthic macrofauna were determined. To compare the studied sites and identify the possible occurrence of anomalous concentrations, trace elements were normalized by Al and linear regressions were also performed. For all trace elements (except Cu), regressions showed a significant correlation (p<0.05) and few outliers (<3% of cases), showing that the concentrations found represent natural values for this bay. In the case of Cu, the highest concentrations were found near small municipalities, which may be associated with domestic sewage. About 60% of the organic compounds occurred at levels below the limit of quantification (<0.26ngg-1). The sum of PAHs was low for all stations, ranging from 1.17 to 313ngg-1. The benthic assemblages also indicated that the CB is a healthy, well-preserved ecosystem that deserves conservation efforts. The integrated use of geochemical and biotic data supported the use of CB as a reference area. Capsule: Organic and inorganic contaminants together with macrobenthic assemblages indicated that Camamu Bay is a pristine, tropical reference area.

Influence of proximity to an urban center in the pattern of contamination by marine debris.

In order to test the relationship between the occurrence of marine debris and the distance from urban areas, nine beaches in the metropolitan area of Salvador, Bahia, Brazil and the adjacent northern coast were studied. Marine debris were collected, sorted in several categories and weighed. It was observed that plastics were numerically the most abundant component of the collected debris. As expected, the beaches closest to Salvador presented the largest density of debris, with the exception of the Porto da Barra beach, which has an efficient public cleaning system and does not have any vegetation, making it difficult to accumulate solid waste. Linear regression analyses showed significant relationships between the distance from the urban center (Salvador) and the number of marine debris per m(2), the total number of debris per beach (abundance), and the diversity of debris types (richness). The results showed that proximity to urban regions was a key factor in the marine debris distribution along the coast.

Inorganic As speciation and bioavailability in estuarine sediments of Todos os Santos Bay, BA, Brazil.

The spatial distribution of As (total As, As (III) and As (V)) in estuarine sediments from the main tributaries of Todos os Santos Bay, BA, Brazil, was evaluated under high and low flow conditions. The concentrations of As were determined using a slurry sampling procedure with hydride generation atomic absorption spectrometry (HG-AAS). The highest concentrations were observed at estuary mouths, and exceeded conservative lower threshold value (Threshold Effects Level; TEL). Due to the oxic conditions and abundance of Mn and Fe (oxyhydr)oxides in the sediments, most inorganic arsenic in the Subaé and Paraguaçu estuaries was present as As (V). Nevertheless, the concentration of As (III) at several locations along the Jaguaripe River were also above the TEL value, suggesting that As may be toxic to biota. In the Subaé estuary, antropogenic activities are the main source of As. At the Jaguaripe and at Paraguaçu estuaries, nevertheless, natural sources of As need to be considered to explain the distribution patterns.

Radionuclide applications in laboratory studies of environmental surface reactions.

The advantages of using radionuclides for laboratory studies of environmental processes include the wide range of element concentrations that can be studied, the capability to simultaneously study several isotopes in a single experiment, the direct applicability to the behaviour of radioactive waste or fallout, and the ability to study the mechanisms, reversibility and kinetics of environmental reactions under controlled conditions. These attributes are demonstrated using specific examples drawn from case studies in Australia, including radionuclide fallout onto tropical soils, the association of trace metals with harbour sediments and the behaviour of uranium in natural and contaminated systems.

Dissolved trace metal distributions in Port Jackson estuary (Sydney Harbour), Australia.

Concentrations of dissolved metals (Cd, Cu, Ni, Mn and Zn) were determined for summer and winter, under low-flow conditions in Port Jackson, a microtidal, well-mixed estuary in south-east Australia. Mean concentrations of Cd (0.04+/-0.02 microg/l), Ni (0.86+/-0.40 microg/l), Mn (20.0+/-25 microg/l) and Zn (6.47+/-2.0 microg/l) were below water quality guidelines. Concentrations of Cu (1.68+/-0.37 microg/l), however, slightly exceeded recommended values. Dissolved Ni and Mn behaved mostly conservatively, whereas Cd, Cu and Zn showed mid-estuarine maxima. Peaks in Cd, Cu and Zn concentrations were located in the upper estuary, independent of the salinity and suspended particulate matter loading, and were consistent with anthropogenic inputs of metals in the estuary. Concentrations of dissolved Cu were highest in summer, whereas concentrations of Cd, Ni and Mn were significantly lower in summer than winter (P< or =0.05). The increase in temperature and biological activity during summer explained the seasonal variation. The sequence of log K(d) values (20-30 salinity) was Mn>Zn>Cu>Ni. These results give unique information concerning the contemporaneous distribution of dissolved trace metals in the Port Jackson estuary and they provide a data set against which the long-term contamination may be assessed.

Kinetics of trace element uptake and release by particles in estuarine waters: effects of pH, salinity, and particle loading.

The uptake and release of 109Cd, 51Cr, 60Co, 59Fe, 54Mn, and 65Zn were studied using end-member waters and particles from Port Jackson estuary, Australia. The kinetics of adsorption and desorption were studied as a function of suspended particulate matter (SPM) loading and salinity. Batch experiments showed that the position and slope of the pH edges are dependent on the metal and on the salinity of the water (except for Mn). The general effect of salinity was to move the adsorption edge to higher pH values, with the greatest change being found for Cd. Most of the metals showed relatively simple kinetics with an increase in uptake as a function of time and suspended particle concentrations. The time dependence of Cd uptake was more complex, with an initial adsorption phase being followed by strong mobilization from the suspended sediments, explained by chlorocomplexation and competition with seawater major cations. The reversibility of the sorption decreased in the order Co>Mn>Zn>Cd>Fe>Cr. The percentage of adsorbed metal released in desorption experiments was greater in seawater than freshwater for Cd, Zn, and Co. These results are important in understanding the cycling of pollutants in response to pH, salinity, and particle concentrations in estuarine environments. In addition, they give valuable insight into the important mechanisms controlling the partitioning of heavy metals in the Port Jackson estuary.

Trace metal and total suspended solids concentrations in freshwater: the importance of small-scale temporal variation.

The temporal variation in the concentrations of particulate trace metals (Cu, Pb and Zn) and total suspended solids (TSS) was examined in three rivers that drain into the Port Jackson estuary, Australia, using a nested, hierarchical sampling design. Sampling was conducted between March and June 1999, under low flow conditions. The sampling design incorporated four temporal scales (hours, days, weeks and months). It was considered that hours, days, weeks and months were representative of such time scales and could be analyzed as random, nested sources of variation in an analysis of variance (ANOVA). Significant variation was found at temporal scales ranging from hours, within the same day, to months. The amount and scales of variation differed between particulate trace metals and TSS concentrations and between rivers. In many cases, differences between small-scale were as important as differences between months. The results suggest that higher anthropogenic influences cause higher variability at small temporal scale. Results indicate the need for nested sampling designs to be incorporated into studies of temporal variation in order to unconfound small-scale temporal variation. The conclusions of this study are likely to be applicable to other water quality variables and pollutants.