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.

Soils and sediments of the Thua Thien-Hue Province (central Vietnam): recognizing trace element sources and the likely influence of natural events.

Trace element concentrations have been measured in soil and sediment samples taken from the Thua Thien Hue (TT-H) Province and the Tam Giang-Cau Hai (TG-CH) Lagoon in 2002 and 2004. Results show that the lagoon is only slightly contaminated by elements such as Ag, Cd, Cr, Cu, Ni, Pb and Zn, whereas As, probably naturally enriched in this Asian region, reaches values above the lowest internationally accepted sediment quality guidelines. Concentrations in soils are ascribable to natural sources and distributions in the TG-CH Lagoon are mainly influenced by river inputs, with Ag and Cd undergoing estuarine desorption processes. However, concentration-depth profiles of most trace elements in sediments show a recent increasing trend that might be linked to the economic development of the area. The comparison of porosity and (210)Pb depth profiles (confirmed also by Cd and As) from repeated samplings of the same core locations in the TG-CH Lagoon seems to account for a loss of 5-10 cm of surficial sediment that took place during the time interval between the two samplings. It is hypothesized that extreme meteorological events (e.g. a major typhoon that hit the area in November 2003) could be responsible for such sediment displacement.

Polychlorinated biphenyls in two salt marsh sediments of the Venice Lagoon.

Polychlorinated biphenyls (PCBs) were measured in two dated salt marsh cores of the Venice Lagoon to assess their input chronology and to evaluate the importance of atmospheric deposition as a source. Sampling sites were chosen in order to evidence the differences between areas located leeward and windward with respect to inputs originating in both the city of Venice and the industrial area. Concentrations of PCB indicators (0.13-15.6 ng g⁻¹) increased gradually from the 1930s, reached maxima from the 1950s to the late 1970s, and then decreased. PCB loadings to marshes are driven by both the atmospheric deposition and the resuspension of subtidal sediments, this latter being more important for heavier congeners. The downwind marsh recorded higher fluxes (0.06-9.72 ng cm⁻² year⁻¹) than the upwind one (0.01-0.53 ng cm⁻² year⁻¹). Recent fluxes are rather consistent with bulk deposition measurements. A higher contribution of CB-101 and CB-118 was detected in the intermediate layers of the downwind site, suggesting a different PCB source for the corresponding time interval. In the other marsh, PCBs showed a rather constant composition at all levels (mostly CB-153, CB-138 and CB-180), accounting for a regional influence. Deep layers showed an enrichment of higher chlorinated congeners at both sites, whereas recent samples conserve the patterns typical of surficial and subsurficial subtidal sediments. The scientific approach adopted in this research can be considered as a sort of methodological procedure for the determination of fluxes and pathways of PCBs through the study of marsh cores.

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.

Pollution historical trends as recorded by sediments at selected sites of the Venice Lagoon.

Polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and hexaclorobenzene (HCB) were determined in three sediment cores of the Venice Lagoon: I1, from the San Giuliano Canal that is likely the main source of pollutants for the study area; E, representing the lagoon sediment of the zone of Campalto; and M3, typical of a salt marsh environment and mostly subject to atmospheric inputs. Maximum concentrations were found in core I1: 25-1858 ngI-TE kg(-1) (PCDD/Fs), 1.7-13 microg kg(-1) (HCB), and 107-717 microg kg(-1) (PCBs) are surficial and peak values, respectively. The lagoon sediment (E), is much less contaminated: 24-47 ngI-TE kg(-1) for PCDD/Fs, 2.3-3.6 microg kg(-1) for HCB, and 56-203 microg kg(-1) for PCBs, whereas M3 shows the lowest values: 1.6-6.0 ngI-TE kg(-1) for PCDD/Fs, 0.3-0.6 microg kg(-1) for HCB, and 7.1-39 microg kg(-1) for PCBs. In any case, the recent trend is toward a decrease of pollutant concentration. The chronology of cores E and M3 is based on both 210Pb and 137Cs activity-depth profiles. The maximum concentrations of PCDD/Fs, HCB, and PCBs correspond to the years 1949, 1980, and 1968, respectively. The homologue profiles of PCDD/Fs confirm that I1 has been subject to an industrial source while the other sites also recorded significant contributions, changing over time, of octachlorinated dioxin from combustion. A comparison of the pollutant inventories, all normalised to 210Pb inventories, suggests that the atmospheric contribution to the contamination of the area of Campalto is low: the upper limits range from 6% (PCDD/Fs) to 17% (HCB).

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.

Distribution of heavy metals in sediments of the Venice Lagoon: the role of the industrial area.

We sampled eighteen stations in the lagoon and nine in the canals of the industrial area of Porto Marghera. At each lagoon site a short core, 10 cm long, was taken and immediately extruded to obtain four slices 2.5 cm thick. Surficial sediment samples from the canals were 2-8 cm thick. Samples were analysed for As, Cd, Hg, Pb and Zn after acid extraction. Maximum values are seen in sediments taken from the oldest part of the industrial area (up to 132, 70, 48, 929, 8295 microg g(-1) for As, Cd, Hg, Pb and Zn, respectively), whereas the highest concentrations in the lagoon are much lower (25, 5.0, 2.3, 114, 1115 microg g(-1) for As, Cd, Hg, Pb and Zn, respectively). Metal distributions are not driven by sediment characteristics, such as grain size composition and organic carbon content: the strong gradients reflect the relative importance of the sources. In fact, a series of factories have been treating minerals for many years for the production of metals and chemicals. Concentration-depth profiles in lagoon sediments suggest that the contamination is decreasing, thus confirming the trends shown by previous core data. Since the release of metals from the industrial plants has been reduced, the polluted sediments stored in the industrial canals are presently the most likely source of toxic metals to the lagoon environment. The influence of this source can be seen in the still high levels found in the lagoon sample closest to the industrial area.

Heavy metals in marine coastal sediments: assessing sources, fluxes, history and trends.

Examples are presented from the Adriatic Sea, the Ligurian Sea and the Venice Lagoon to illustrate different approaches to the study of anthropogenic metals in marine coastal sediments. These examples refer to studies of areal distribution and transport mechanisms, individuation of the sources, sediment dating, chronology of the fluxes, present and past trends. In particular, some of the findings achieved in studying the Venice Lagoon are discussed from the point of view of anthropogenic changes both in sediment composition and contaminant fluxes.

Historical pattern and mass balance of trace metals in sediments of the northwestern Adriatic Sea Shelf.

In view of the recent action in Marine Strategy Framework Directive, reconstructing the history of anthropogenic metal inputs and calculating the budgets for the northwestern part of the Italian Adriatic basin can provide a benchmark for comparison with new evidences and enlighten recent environmental changes. Among the metals, the attention was focused on Pb and Zn, as they provide the most significant anthropogenic signals. In 1988, areal distributions clearly identified the Po, Adige and Brenta rivers as the main sources of contaminants. The study area was divided in three compartments. The area in front of the Po delta represented a sink for metals but the accumulation of Zn and Pb integrated over the entire study area suggests an effective export throughout southern boundary. Most concentration-depth/year profiles in cores showed an upward increase from the Italian Unification (1861), with a still significant anthropogenic supply at the time of sampling.

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.

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.

Historical PCB fluxes in the Mexico City Metropolitan Zone as evidenced by a sedimentary record from the Espejo de los Lirios lake.

The accumulation of PCBs over time was studied in a sediment core collected from Espejo de los Lirios, an ecological reserve located within the heart of Cuatitlan Izcalli, in the Northern part of Mexico City Metropolitan Zone. A (210)Pb-derived chronology, was used to reconstruct the historical PCB fluxes to the site during approximately 84 yr (1911-95). The highest input fluxes occurred in the 1977, after a significant increase after the late 1940s. This trend is clearly the consequence of the increasing emissions that are related to the onset of industrial activities starting from early 1970s. A phase of decrease, after the ban of the use in open systems, ended in 1989 and in 1995, at the time of sampling, the trend was toward a new increase to the highest levels. A reconstruction of PCB atmospheric concentration from sedimentary fluxes is attempted; and the estimate suggests that PCBs concentrations in the air of the Cuautitlán Izcalli seem not of concern. Nonetheless, the contamination levels found in the sediments are relatively high, reaching values above the threshold effect level (TEL) guidelines and, in two cases, close to the probable effect level (PEL) which mean that some adverse effects on the fauna may have occurred all over the time interval represented by the core.

Recent sedimentary history of organic matter and nutrient accumulation in the Ohuira Lagoon, northwestern Mexico.

(210)Pb-derived sediment accumulation rates, as well as a suite of geochemical proxies (Al, Fe, delta(13)C, delta(15)N), were used to assess the time-dependent variations of C, N, and P fluxes recorded in two sediment cores collected at Ohuira Lagoon, in the Gulf of California, Mexico, during the last 100 years. Sedimentary C, N, and P concentrations increased with time and were related to land clearing, water impoundment, and agriculture practices, such as fertilization. C:N:P ratios and delta(13)C suggested an estuarine system that is responsive to increased C loading from a N-limited phytoplankton community, whereas delta(15)N values showed the transition between an estuarine-terrestrial to an estuarine-more marine environment, as a consequence of the declining freshwater supply into the estuary due to the channeling and impoundment of El Fuerte River between 1900 and 1956. The recent increases in nutrient fluxes (2- to 9-fold the pre-anthropogenic fluxes of C and N, and 2 to 13 times for P) taking place in the mainland from the 1940s, were related to the expansion of the intensive agriculture fields and to the more recent development of shrimp farming activities.