Silvia Giuliani

PBDEs and PCBs in sediments of the Thi Nai Lagoon (Central Vietnam) and soils from its mainland.

Concentration and distribution of PCBs, PCB 11, and PBDEs in both surficial sediment and soil samples, taken from a zone subject to recent accelerated development, were investigated to assess the environmental quality and understand both natural and anthropogenic processes that influence contaminant behaviors. Values of PCB and PBDE are in the lower range of those reported in literature, typical of low impacted coastal zones. This could be due to efficient processes of resuspension and removal. Contaminants in the lagoon showed higher concentrations in sediments from sites close to the city and the outfalls of the industrial area, while soils showed maximum values in the northern samples. In addition, congener patterns and statistical analyses suggest the presence of effective degradation processes, especially for PBDEs, with the exception of the most concentrated samples that may indicate a direct input. PCB 11 is a significant component (up to 18%) in most lagoon sediments. Its presence is strongly associated with fine particles, thus the distribution seems to be driven mainly by the system hydrodynamic and does not trace the sources. Due to evaporation, only flooded agricultural soils show a similar relative abundance of this congener.

An Integrated Approach to the Assessment of Pollutant Delivery Chronologies to Impacted Areas: Hg in the Augusta Bay (Italy)

Assessing pollution levels and trends in heavily impacted environments is important but hardly achievable due to the difficulty of recovering suitable undisturbed sediment records. An integrated approach is here presented to solve this kind of problem. It was adopted in the Augusta Bay (Italy) for the study of Hg historical inputs and present trends. Archive information on dredging and mud disposal, together with bathymetry and high-resolution seismic profiles, were used to identify suitable sampling sites. Undisturbed sediment cores were collected in the port and bay. Sediments were analyzed for depth distributions of radiotracers ((210)Pb and (137)Cs), Hg, and main sediment parameters (magnetic susceptibility, grain size, dry bulk density, mineralogy, and organic carbon and nitrogen contents). Hexachlorobenzene (HCB) was also analyzed as an additional time tracer, since its production history in the area was well-known. Results show that peak Hg contamination (up to 575 mg·kg(-1)) was reached in the 1970s. Technological improvements and waste treatment in the following years determined a consistent decrease, but high concentrations still affect surficial sediments (0.25-92 mg·kg(-1)). Hg-HCB correlation suggests that this situation is likely the effect of resuspension and redistribution of deep sediments by dredging and naval traffic.

Recognizing different impacts of human and natural sources on the spatial distribution and temporal trends of PAHs and PCBs (including PCB-11) in sediments of the Nador Lagoon (Morocco).

The Nador Lagoon holds a major interest in present-day Moroccan socioeconomic development. This environment is exposed to a number of potential polluting sources, such as mine tailings, urban and industrial dumping, and untreated wastewater inputs from surrounding cities. The aim of this study was to assess concentrations and trends of persistent contaminants such as PCBs and PAHs and to identify their origin. The non-Aroclor PCB-11 was determined for the first time in the lagoon sediments. Chronology and source assessment helped identifying the timing and nature of inputs and post-depositional processes controlling the two classes of contaminants: PAHs present a typical mixed petrogenic signature, with the exception of sediments deposited in the period 1930-1960 near the city of Nador, when pyrogenic inputs prevailed; PCBs show signs of microbial anaerobic degradation from 1950 to 1990, probably linked to changing hydrodynamic conditions in the South-Western part of the lagoon where agricultural inputs are dominant. The presence of PCB-11 is linked to specific productions and might be affected by degradation processes. Presently, different land uses (e.g., urban and agricultural areas) appear to be the key factors in controlling the level and composition of PAHs and PCBs in lagoon sediments. Total PAH and PCB levels are low (from 21.6 to 108 ng g(-1) and from 2.50 to 20.7 ng g(-1), respectively) but recent increasing values and the potential threat to humans and biota require continuous and constant monitoring.

Polychlorinated biphenyls in sediments of selected coastal environments in northern Morocco

disturb them, e.g., typhoons, storm surges, dredging activities etc. Their movement into biotic communities within this area predominantly occurs via the sediment ingester-suspension feeder-carnivore route rather than through primary producers and secondary trophic level consumers. From a human health standpoint, lead was identified as the element of greatest concern with advisory excedences noted in bivalves from the dump (Site 2) northwards to Lower Base Channel (Site 6). With the exception of copper in Q. palatum from Site 2, trace metal levels in all other biotic representatives were well below critical threshold levels of concern when weighed against existing USA advisories (USEPA, 1986; USFDA, 1998) and food standards of other countries (Nauen, 1983).

PCBs in Central Vietnam coastal lagoons: levels and trends in dynamic environments

PCBs were analysed in surficial sediments and selected sediment cores collected between 2002 and 2008 in Central Vietnam coastal lagoons. The aim was to determine contamination levels and trends, and to evaluate the effects of anthropogenic pressures and natural events. Samples were mostly fine-grained with low total PCB concentrations (0.367-44.7 μg kg(-1)). Atmospheric transport and post depositional processes modify to some degree the fingerprint of PCB inputs to the environment favouring the predominance of 3, 4 and 5 chlorinated congeners. The similarity of congener distributions in contemporary surficial samples also suggests the presence of a unique source over the entire study area, probably connected to mobilisation and long range transports from land-based stocks. The removal of consistent sediment layers is hypothesised based on repeated samplings of the same area. Natural meteorological events (such as typhoons) are suspected to be responsible for these sediment losses.

PCDD/Fs in sediments of Central Vietnam coastal lagoons: In search of TCDD.

Samples from nine Central Vietnam coastal lagoons, together with three soils and sediments collected in two freshwater reservoirs of the Thua Thien-Hué province, were analysed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Total concentrations are low, from 192 to 2912 pg g(-1) and depth profiles in Tam Giang-Cau Hai (TG-CH) sediment cores show only minor changes over time in PCDD/F input and composition. Octachloro dibenzo-p-dioxin (OCDD) is the prevailing congener (approximately 90%), indicating combustion as the main PCDD/F source to these coastal systems, whereas natural formation might be partly responsible for the presence at depth. 2,3,7,8-Tetrachloro dibenzo-p-dioxin (TCDD), largely sprayed together with Agent Orange over the study areas during the war (1961-1971), is absent or very low. This result supports the hypothesis of strong degradation soon after spraying. Multivariate statistical analyses account for the presence of local, short-range sources as observed in the northern part of the TG-CH lagoon.

Examination of the uncertainty in contaminant fate and transport modeling: a case study in the Venice Lagoon.

A Monte Carlo analysis is used to quantify environmental parametric uncertainty in a multi-segment, multi-chemical model of the Venice Lagoon. Scientific knowledge, expert judgment and observational data are used to formulate prior probability distributions that characterize the uncertainty pertaining to 43 environmental system parameters. The propagation of this uncertainty through the model is then assessed by a comparative analysis of the moments (central tendency, dispersion) of the model output distributions. We also apply principal component analysis in combination with correlation analysis to identify the most influential parameters, thereby gaining mechanistic insights into the ecosystem functioning. We found that modeled concentrations of Cu, Pb, OCDD/F and PCB-180 varied by up to an order of magnitude, exhibiting both contaminant- and site-specific variability. These distributions generally overlapped with the measured concentration ranges. We also found that the uncertainty of the contaminant concentrations in the Venice Lagoon was characterized by two modes of spatial variability, mainly driven by the local hydrodynamic regime, which separate the northern and central parts of the lagoon and the more isolated southern basin. While spatial contaminant gradients in the lagoon were primarily shaped by hydrology, our analysis also shows that the interplay amongst the in-place historical pollution in the central lagoon, the local suspended sediment concentrations and the sediment burial rates exerts significant control on the variability of the contaminant concentrations. We conclude that the probabilistic analysis presented herein is valuable for quantifying uncertainty and probing its cause in over-parameterized models, while some of our results can be used to dictate where additional data collection efforts should focus on and the directions that future model refinement should follow.

Sediment pollution and dynamic in the Mar Piccolo of Taranto (southern Italy): insights from bottom sediment traps and surficial sediments

Major and trace element, PAH, and PCB concentrations were measured in surface sediments and particles from sediment traps collected in the First and Second Basin of the Mar Piccolo (Gulf of Taranto) in two periods (June–July and August–September, 2013). The aim of the study was to evaluate pollution degree, sediment transport and particle redistribution dynamic within the area. Results confirm the higher contamination of sediments from the First Basin observed by previous researches, particularly for Cu, Hg, Pb, total PAHs, and total PCBs. Advective transport from the First to the Second Basin appears to be the leading transfer mechanism of particles and adsorbed contaminants, as evidenced by measured fluxes and statistical analyses of contaminant concentrations in surficial sediments and particles from sediment traps. Long-range selective transports of PAHs and microbial anaerobic degradation processes for PCBs have been also observed. These results are limited to a restricted time window but are consistent with the presence of transport fluxes at the bottom of the water column. This mechanism deserves further investigation and monitoring activities, potentially being the main responsible of pollutant delivering to the less contaminated sectors of the Mar Piccolo.

Can PBDE natural formation and degradation processes interfere with the identification of anthropogenic trends and sources? Evidences from sediments of the Nador Lagoon (Morocco).

This paper presents the first results related to PBDE concentrations in sediments of the Nador Lagoon (N-E Morocco), an area endangered by different pollutant sources. Analyses were performed by HRGC-LRMS and confirmed by HRGC-HRMS on selected samples. Total surficial concentrations were 0.059-8.2ngg(-1). The maxima were found close to Nador City. Along the sedimentary records, the highest total concentrations (11 and 2.2ngg(-1)) were found at depths corresponding to times (1930s-1950s) when these chemicals were not yet produced. Dehydroxylation or demethoxylation of naturally occurring structural analogues of PBDEs under reducing conditions was suggested. BDE-47 dominated the congener compositions, while BDE-209, when present, could be detected only by HRGC-HRMS, proving that analytical degradation modified the original assemblage. Microbial anaerobic degradation could have changed congener compositions in sediments deposited from the 1970s to the 2000s. Current values are not harmful, but increasing trends call for constant monitoring.

The impact of the 1999 Mw 7.4 event in the İzmit Bay (Turkey) on anthropogenic contaminant (PCBs, PAHs and PBDEs) concentrations recorded in a deep sediment core

The 1999 Mw 7.4 earthquake triggered a tremendous human tragedy and had a great social impact over the population of the İzmit Bay, one of the most industrialized area of Turkey. Although the successive environmental disasters were well documented, information on its sedimentary record is lacking. The present research aims at filling this gap, through the analysis of organic contaminants (PCBs, PAHs, and PBDEs) in a dated sediment core collected in the depocenter of the Karamürsel Basin in 2005. Profiles of total PCBs and total PAHs overlap the timing of industrialization in the area (starting in the 1960s) with values increasing as the population and the number of industrial plants grew larger. Profiles for PBDEs are in accordance with increasing urban inputs but are probably affected by processes of natural formation and post-depositional mixing. The continuous sedimentary record is interrupted at a level dating back to 1980 due to the erosion caused by the 1999 earthquake, having removed a 5-7cm thick sediment layer. Contaminant concentrations in the deepest 10-15cm of a 30cm thick seismo-turbidite unit, triggered by the 1999 event, increase with the progressive fining up and evidence massive transport of sediments from coastal, more polluted sites of the north-eastern Karamürsel shelves and shores. Additional inputs of PAHs are also evident, originating from a fire at the oil refinery that followed the shaking. The effects of the earthquake generated tsunami, its backwash fluxes and the following seiches are not uniquely displayed by each class of contaminants, and they could probably reflect successive inputs deriving from different parts of the basin that are subject to anthropogenic impacts of different nature. Concentrations measured at the top of the core are consistent with an unvaried input of pollutants in the period 1980-2005.