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Coastal wetland ecosystems are of utmost importance in regulating the mobility and distribution of elements in water and sediments, being the flooding by tidal events a recurrent process that strongly controls the hydrodynamics of the system. The aim of this work is to assess the control of the tidal regime and anthropogenic influence on the dynamics of some trace metals in water and sediments in the Punta Lara Natural Reserve situated in the Río de la Plata littoral. For that purpose, relationship between tidal flows, surface water and groundwater was evaluated. Also, hydrochemistry was analyzed based on the study of major ions and trace metals, being the presence of high concentrations of elements in groundwater, such as Fe and Mn, probably favoured by redox processes associated with organic matter decomposition in the water - sediment interaction. Sediments in the wetland register deficient to minimal enrichment in most of the studied trace metals despite the numerous contributions that the Río de la Plata receives in relation to dissolved and particulate trace metals from diverse anthropogenic contributions. Despite that, there is a moderate enrichment in Pb and Cr in the surface sediments of the wetland. The data analyzed within the natural reserve in relation to the chemical composition of the water and sediments of the coastal wetland showed the strong influence of the tidal regime over the area.

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Terminos Lagoon (TL), in the southern Gulf of Mexico, has been under intensive anthropogenic pressure (e.g., oil-industry development) since the 1970s. Historical changes in flux ratios of potentially toxic elements (PTEs; As, Cd, Cr, Cu, Ni, Pb, V, Zn) were, for the first time, assessed inside TL by using 210Pb-dated sediment cores. Sediments showed minor enrichments for Cd, Ni, Pb, and V. However, according to international benchmarks, the As, Cr, Cu, and Ni concentrations could pose a risk for benthic biota. Sedimentary processes involved in the accumulation of PTEs were identified through a chemometric approach. Increments in PTEs flux ratios concur with the recent (⁓50 years) and extensive land-use changes, particularly the transport and deposit of materials delivered by rivers. These findings are expected to be used in managing this crucial natural resource, the larger Mexican coastal lagoon ecosystem, to mitigate the effects of global change.

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Spatial and temporal variations of mercury (Hg) concentrations, enrichment, and potential ecological risks were studied in a suite of lead-210 (210Pb) dated sediment cores from 13 Wider Caribbean Region coastal environments. Broad variability of Hg concentrations (19-18761 ng g-1) was observed, encompassing even background levels (38-100 ng g-1). Most Hg concentration profiles exhibited a characteristic upward trend, reaching their peak values in the past two decades. Most of the sediment sections, showing from moderately to very severe Hg enrichment, were found in cores from Havana Bay and Sagua River Estuary (Cuba), Port-au-Prince Bay (Haiti), and Cartagena Bay (Colombia). These were also the most seriously contaminated sites, which can be considered regional Hg 'hotspots'. Both Havana Bay and Port-au-Prince Bay reportedly receive waste from large cities with populations exceeding 2 million inhabitants, and watersheds affected by high erosion rates. The records from the Sagua River Estuary and Cartagena Bay reflected historical Hg contamination associated with chloralkali plants, and these sites are of very high ecological risk. These results constitute a major contribution to the scarce regional data on contaminants in the Wider Caribbean Region and provide reference information to support the evaluation of the effectiveness of the Minamata Convention.

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This study assessed the concentrations and sources of natural and anthropogenic aliphatic (AHs) and polycyclic aromatic hydrocarbons (PAHs) in superficial sediments collected along the Patos Lagoon estuary and in sediment cores obtained from the Cassino Beach mud bank. Levels and distribution of n-alkanes indicate terrestrial sources, overlapping with a low amount of petrogenic hydrocarbons (heavy oils). Unresolved complex mixture (UCM) was observed in all samples. On the other hand, the distribution of PAHs in the sediments showed a predominance of pyrolytic over petrogenic sources. In general, hydrocarbons (HCs) contamination in the Patos Lagoon estuary and its adjacent coastal area can be considered low, except for sites near urban or industrial effluents, where moderate to high levels of contamination were found. Concentrations of hydrocarbons were homogeneous throughout the sediment cores, suggesting that mixing processes may have occurred along the layers or that HCs inputs to the mud banks were uniform during the studied deposition period. In addition, the levels and profile of HCs in the coastal sediments were similar to those observed in the estuary. Moreover, the frequent remobilization of sediments from the mud bank towards Cassino beach does not seem to pose any threats to the local biota or beach users since the levels of contamination were relatively low and below the threshold limits of sediment quality guidelines.

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Environmental assessment in marine systems is difficult because most of the time their preindustrial characteristics are not available. Four sediment cores taken in Mejillones bay (northern Chile) were used to establish preindustrial metals concentrations, and to assess the environmental status of this industrialized zone. According to historical documents, the beginning of the industrial era start in 1850 CE. Considering this, the preindustrial concentration of some metals was established, by mean of a statistical approach. Most of the metals increase their concentration from the preindustrial to the industrial period. Environmental assessment showed an enrichment of Zr and Cr, a moderately polluted condition, and a low probability of toxic effect on the biological communities. The preindustrial values derived from sediment cores are a good tool to evaluate the environmental condition of Mejillones bay. However new information (backgrounds with a higher spatial representativity, toxicological threshold, and others) it is necessary to improve the environmental assessment of this environment.

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The present study determined total mercury (Hg) in four 210Pb dated sediment cores to assess the historical anthropogenic Hg accumulation in the Santos estuary, Southeastern Brazil. Background levels were identified using the deepest sections of the cores, corresponding to pre-industrial ages. Mercury distribution in the sediment cores (0.02-2.64 mg kg-1) presented a large spatial and temporal variation. Contamination is highest in the upper estuary and indicates that the industrial hub, especially a chlor-alkali plant is the primary source of Hg. A contaminant trap effect is observed in this area associated with high fine sediment accumulation and Hg fluxes. The contamination pattern indicates that the regions not affected by direct inputs are influenced by reworking, resuspension, and transport of contaminated sediments by tidal flows. The Hg enrichment in the upper layers of the sediment cores demonstrates that the environmental actions fulfilled in the 1980s were insufficient to control Hg pollution in the Santos estuary.

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The sediment contamination by trace metals in coastal aquatic ecosystems is a worldwide environmental problem, since metals can be toxic, persistent, and bioaccumulated. In case of natural events, such as storms, or anthropogenic activities, like dredging, the sediment resuspension to the water column occurs and can solubilize metals, probably increasing their bioavailability and consequently the risk to aquatic life. This study evaluated the bioavailability on reactive trace metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in estuarine sediments from Iguaçu and Meriti Rivers, both in the drainage basin of Guanabara Bay (Rio de Janeiro, Brazil). Additionally, a discussion about the anthropogenic interference throughout time of six short sediments cores, calculating three different indexes (contamination factors, CF; potential ecological risk index for a single heavy metal, Eif for short; potential ecological risk, PERI) was performed. It was considered as reactive phase, the metal concentrations obtained using a weak acid extraction (in HCl 1 mol L-1 solution). Zn presented high concentrations after resuspension, being above effect range medium (ERM) (52.81 to 1337.4 mg kg-1). The CF indicated very high contamination degree for Cu (14.62 to 17.96) and Zn (27.80 to 35.85) for both rivers. The Eif for short presented higher risk to Cu and Zn for Iguaçu and Meriti rivers. PERI index classified Meriti River samples as severely contaminated (238.10 to 351.62).

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The historical variation of sedimentation rate was investigated in five cores collected from the Itanhaém watershed main rivers, the second largest coastal watershed of the São Paulo state, Brazil, using the lead-210 radioisotope as a geochronometer. The main characteristics of the rivers' waters and sediments were determined in order to support the geochronological analysis results and associate sediments with possible source areas. In this context, the fluvial waters' general classification indicated the facies sulfated or chlorinated sodium in the winter and summer seasons, except for the Branco river waters in summer, which were classified as calcium or magnesium bicarbonate. A longitudinal salinity gradient was found in the downstream river courses, under greater marine influence, with the ions Cl-, Na+, SO42+, Mg2+, Ca2+, and K+ being most common in the waters. Silica is the predominant constituent in the sediment cores and is inversely related to the organic matter (OM) presence. Inverse correlations were also found between silica and other constituents. The watershed sedimentation rates were determined in the range of 0.31 up to 3.97 g/cm2/year and 0.30 up to 3.40 cm/year, highlighting the core extracted from Branco river, which showed the highest sedimentation rate. The profiles corresponding to Preto and Aguapeú rivers presented discontinuities in the sedimentation rates. The discontinuities were dated and would probably be related to the anthropic activities, which intensified in the municipality of Itanhaém around the middle of the twentieth century.

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Due to global warming, in the northeastern semiarid coastal regions of Brazil, regional and global drivers are responsible for decreasing continental runoff and increasing estuarine water residence time, which promotes a greater mobilization of bioavailable mercury (Hg) and allows increasing fluxes and/or bioavailability of this toxic trace element and an acceleration of biogeochemical transformation of Hg. In this work, an application of dendrochemistry analysis (annular tree rings analysis) was developed for the reconstruction of the historical pattern of mercury contamination in a contaminated area, quantifying chronological Hg contamination trends in a tropical semiarid ecosystem (Ceará River Estuary, northeastern coast of Brazil) through registration of mercury concentration on growth rings in specimens of Rhizophora mangle L. and using the assessment in sediments as a support for the comparison of profiles of contamination. The comparison with sediments from the same place lends credibility to this type of analysis, as well as the relationship to the historical profile of contamination in the region, when compared with local data about industries and ecological situation of sampling sites. In order to evaluate the consequences of the described increase in Hg bioavailability and bioaccumulation in aquatic biota, and to assess the biological significance of Hg concentrations in sediments to fish and wildlife, muscle and liver from a bioindicator fish species, S. testudineus, were also analyzed. The results of this work reinforce the indicators previously described in the semiarid NE region of Brazil, which showed that global climate change and some anthropogenic factors are key drivers of Hg exposure and biomagnification for wildlife and humans. Considering the Hg concentration present in the top layers of sediment (~20 cm around 15 to 20 years) with the outer layers in the tree ring cores and in the sediment's cores from Pacoti estuary and the Ceará estuary, overall the data indicate an increase in mercury in recent years in the Hg surface sediments, especially associated with the fine sediment fraction, mainly due to the increased capacity of small particles to adsorb Hg. There was revealed a positive and significant correlation (p < 0.05) between Hg trends in sediments and Hg trends in annular tree rings. This shared Hg pattern reflects local environmental conditions. The Hg concentration values in S. testudineus from both study areas are not restrictive to human consumption, being below the legislated European limit for Hg in foodstuffs. The results from S. testudineus muscles analysis suggest a significant and linear increase in Hg burden with increasing fish length, indicating that the specimens are accumulating Hg as they grow. The results from both rivers show an increase in BSAF with fish growth. The [Hg] liver/[Hg] muscles ratio >1, which indicates that the S. testudineus from both study areas are experiencing an increase in Hg bioavailability. Possible climate-induced shifts in these aquatic systems processes are inducing a greater mobilization of bioavailable Hg, which could allow an acceleration of the biogeochemical transformation of Hg.

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Polycyclic aromatic hydrocarbon (PAH) concentrations were determined in four dated sediment cores collected in mud depocenters of the southern Brazilian continental shelf. Core dating results covered the interval between 1925 and 2017. The total PAH concentrations (ΣPAHs) ranged from 44.69 ng g-1 to 305.43 ng g-1 and were similar between the analysed cores. Fine-grained sediments and total organic carbon (TOC) results did not correlate with the ΣPAHs, indicating that the variations in PAH concentrations are mostly related to variations in sources and emissions. PAH source appointment indicated a high input of a natural compound (perylene) and the predominance of anthropogenic PAHs from coal, biomass, and fuel combustion. Alkylated PAHs presented high contributions throughout all cores. The historical deposition of PAHs was associated with different periods of the socio-economic and industrial development of near coastal cities and reflected very well the history of coal production and consumption in the southern region of Brazil. The low levels of ΣPAHs before 1945 in all analysed cores may be related to the beginning of the industrialization process and the lower urbanization degree in the region. Between 1945 and 1965, the gradual ΣPAHs increase reflects the establishment and enlargement of the southern Brazilian industrial sector. The interval between 1965 and 1990 corresponded to the highest ΣPAHs in three of the four analysed cores. After 1990, a relative decrease in the ΣPAHs was observed in most cores and may be related the multiple cuts of incentives to the industrial usage of coal, as well as to Brazil's efforts in environmental regulation for coal extraction and consumption.

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ICOLLs are extremely sensitive to human activities when it comes to sediment metal and nutrient enrichment. To better understand anthropogenic influences associated with Carapebus ICOLL basin historical land use based in Serra, Great Vitória, ES, Brazil, two sediment cores were studied for trace and major elements, organic matter, C/N ratios, total sulfur, and phosphorus. Two stratigraphic units could be found in the sediment cores, one that is related to urbanization, more specifically sewage discharges, and an older one of lithogenic origin with maritime influence. A transition period was also identified from terrestrial influence (upper plants), probably due to deforestation. The more recent stratigraphic unit is characterized by higher organic and metal contents, while the former one is sandy, enriched in detrital metals and calcite. We derived that the Carapebus ICOLL hydrological regime of recent years was changed by the land-use changes in the watershed, specifically due to a larger sediment loading and subsequent closure of the berm. An originally mesotrophic system, Carapebus Lagoon shows the first signs of eutrophication.

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Faecal sterols and stable isotopes (δ13C and δ15N) from bulk organic matter (OM) were analysed in three sedimentary cores collected in two subtropical bays located in the South Atlantic to evaluate historical trends in the sewage input and to track possible changes in the bulk isotopic composition of OM in recent decades. The values of δ13C and δ15N ranged from -27.4 to -25.0‰ and from 0.5 to 3.9‰, respectively, without a clear trend in the variation over the whole period covered by sediment cores and with no conclusive interpretation of a specific range value typically related to the sewage input for these areas. The maximum coprostanol concentration was 0.19 µg g-1 in the upper 4 cm of one core, which was not considered contaminated by evaluation of the sterols diagnostic ratios. Even at low levels, the coprostanol concentrations followed variations in urban and economical regional development. Baseline values for faecal sterols (in average between 0.03 and 0.05 µg g-1), which may represent a previous non-impacted environment scenarios, were calculated for use in comparative perspectives for future evaluations of the sewage input and contamination.

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The sources and depositional history of OCPs (organochlorine pesticides), PCBs (polychlorinated biphenyls) and PAHs (polycyclic aromatic hydrocarbons) over the last 100years were determined in two sediment cores collected in the Amazon region. It was possible to distinguish two depositional periods along the cores. The first period occurred before extensive anthropogenic effects were registered in the sediments. During this time interval, the concentrations of all OCPs and PCBs were below the detection limits (DL), and the PAH concentrations were low and essentially constant (58.19-124.28ngg-1). The second period starts in the mid-1960s and reflects the increased human influence in the area. The concentrations of OCPs, PCBs, and PAHs increased towards the top of the cores, varying between

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Monitoreo del Ambiente , Hidrocarburos Clorados/análisis , Plaguicidas/análisis , Bifenilos Policlorados/análisis , Hidrocarburos Policíclicos Aromáticos/análisis , Contaminantes Químicos del Agua/análisis , Brasil , Estuarios

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The Gulf of Mexico is considered one of the world's major marine ecosystems, supporting important fisheries and habitats such as barrier islands, mangrove forests, seagrass beds, coral reefs etc. It also hosts a range of complex offshore petroleum exploration, extraction, and refining industries, which may have chronic or acute impacts on ecosystem functioning. Previous work on the marine effects of this activity is geographically incomplete, and has tended to focus on direct hydrocarbon impacts, while impacts from other related contaminants (e.g. heavy metals, salt-rich drilling muds) which may be discharged from oil facilities have not been widely assessed. Here, we examine historical trace element accumulation in marine sediments collected from four sites in the Tamaulipas shelf, Gulf of Mexico, in the area of the Arenque oil field. Dated sediment cores were used to examine the sources, and historical and contemporary inputs, of trace metals (including those typically present in oil industry discharges) and their potential biological impact in the Tamaulipas aquatic environment over the last 100years. CaO (i.e. biogenic component) normalized data showed increasing V, Cr, Zn, Cu, Pb, Zr and Ba towards the sediment surface in three of the four cores, with Ba and V (based on an adverse effect index) possibly associated with adverse effects on organisms. Dated Ba/CaO profiles show an increase of 30-137% after opening of oil installations in the study area, and can be broadly correlated with increasing oil industry activities across the wider Gulf of Mexico. Data do not record however a clear enhancement of Ba concentration in sediment cores collected near to oil platforms over more distal cores, indicating that any Ba released from drilling platforms is incorporated quickly into the sediments around the drilling sites, and once this element has been deposited its rate of resuspension and mobility is low. CAPSULE ABSTRACT: Sediment core data from the Tamaulipas shelf show the influence of oil industry activities on selected trace element concentrations, with Ba/CaO broadly correlating with increasing oil industry activities across the wider Gulf of Mexico.

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Tributyltin (TBT) concentrations near a marina complex in Benner Bay on St. Thomas, US Virgin Islands, were elevated relative to other areas in a larger study of the southeastern shore of the island. At the request of the USVI Coastal Zone Management Program, sediment cores and surface sediment samples were collected to better define the extent and history of TBT deposition in the vicinity of Benner Bay. The sediment cores were sectioned into 2-cm intervals and dated with 210Pb and 137Cs. The core sections and the surface samples were analyzed for butyltins and 16 elements. Deposition rates varied from 0.07-5.0 mm/year, and were highest in the marina complex. Core ages ranged from 54 to 200 years. The bottoms of the cores contained shell hash, but the top layers all consisted of much finer material. Surface concentrations of TBT exceeded 2000 ng Sn/g (dry weight) at two locations. At a depth of 8 cm TBT exceeded 8800 ng Sn/g in the marina complex sediment. Based on the ratio of tributyltin to total butyltins, it appears that the marina sediments are the source of contamination of the surrounding area. There is evidence that vessels from neighboring islands may also be a source of fresh TBT. Copper concentrations increase over time up to the present. Gradients of virtually all metals and metalloids extended away from the marina complex. NOAA sediment quality guidelines were exceeded for As, Pb, Cu, Zn, and Hg.

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Spectroscopic and chromatographic techniques can be used together to evaluate hydrocarbon inputs to coastal environments such as the Paranaguá estuarine system (PES), located in the SW Atlantic, Brazil. Historical inputs of aliphatic hydrocarbons (AHs) and polycyclic aromatic hydrocarbons (PAHs) were analyzed using two sediment cores from the PES. The AHs were related to the presence of biogenic organic matter and degraded oil residues. The PAHs were associated with mixed sources. The highest hydrocarbon concentrations were related to oil spills, while relatively low levels could be attributed to the decrease in oil usage during the global oil crisis. The results of electron paramagnetic resonance were in agreement with the absolute AHs and PAHs concentrations measured by chromatographic techniques, while near-infrared spectroscopy results were consistent with unresolved complex mixture (UCM)/total n-alkanes ratios. These findings suggest that the use of a combination of techniques can increase the accuracy of assessment of contamination in sediments.

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To determine the internal phosphorus load (IPL) as a function of redox potential (Eh) in a Mexican reservoir, the results from a phosphorus (P) release experiment were extrapolated to temporal and spatial variations of Eh in sediments, and an IPL-Eh of 24.2 ± 2.5 t/yr was obtained. This result is compared with the P mass balance (MB) in the reservoir, where the IPL-MB is determined as the difference between P inputs to the reservoir and the outputs. Inputs of P are the sum of the external P load from the hydrological basin, the IPL, and P in atmospheric precipitation; outputs of P are the sum of sedimented P, and the removal of P in water and biomass, and the resulting IPL-MB, is 26.4 ± 4.9 t/yr. In addition, P concentrations in sediment cores (SCs) are analyzed, and the historical release of P from sediments determined, resulting in an IPL-SC of 23.5 ± 1.4 t/yr. The different IPL results are similar, as average values are within the standard deviation of IPL-MB. It is concluded that analysis of the variations in Eh in sediments allows determination of the reservoir's IPL. Six-weekly IPL-Eh and IPL-MB values are analyzed, and it can be seen that IPL occurs mainly during the period from May to August, when the water column is thermally stratified.

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Processes involving heavy metals and other contaminants continue to present unsolved environmental questions. To advance the understanding of geochemical processes that involve the bioavailability of contaminants, cores where collected in the Rodrigo de Freitas lagoon, and analyzed for bacterial activity and metal concentrations. Results would suggest an extremely reducing environment where organic substances seem to be the predominant agents responsible for this geochemical process. Analytical data showed sulphate reduction to be the main agent driving this process, since this kind of bacteria was found to be active in all of the samples analyzed. Esterase enzyme production did not signal the influence of heavy metals and hydrocarbon concentrations and heavy metals were found to be unavailable for biota. However, correlation between results for bacterial biomass and the potentially mobile percentage of the total Ni concentrations would suggest a negative impact.

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Processes involving heavy metals and other contaminants continue to present unsolved environmental questions. To advance the understanding of geochemical processes that involve the bioavailability of contaminants, cores where collected in the Rodrigo de Freitas lagoon, and analyzed for bacterial activity and metal concentrations. Results would suggest an extremely reducing environment where organic substances seem to be the predominant agents responsible for this geochemical process. Analytical data showed sulphate reduction to be the main agent driving this process, since this kind of bacteria was found to be active in all of the samples analyzed. Esterase enzyme production did not signal the influence of heavy metals and hydrocarbon concentrations and heavy metals were found to be unavailable for biota. However, correlation between results for bacterial biomass and the potentially mobile percentage of the total Ni concentrations would suggest a negative impact.

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Processes involving heavy metals and other contaminants continue to present unsolved environmental questions. To advance the understanding of geochemical processes that involve the bioavailability of contaminants, cores where collected in the Rodrigo de Freitas lagoon, and analyzed for bacterial activity and metal concentrations. Results would suggest an extremely reducing environment where organic substances seem to be the predominant agents responsible for this geochemical process. Analytical data showed sulphate reduction to be the main agent driving this process, since this kind of bacteria was found to be active in all of the samples analyzed. Esterase enzyme production did not signal the influence of heavy metals and hydrocarbon concentrations and heavy metals were found to be unavailable for biota. However, correlation between results for bacterial biomass and the potentially mobile percentage of the total Ni concentrations would suggest a negative impact.

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