Distribution and source of plutonium in sediments from the southern Gulf of Mexico.

Here, we report on new data (75 analyses) of plutonium (Pu) isotopes to elucidate activity concentrations, inventories, sources, and their transport from the ocean surface to the seafloor from a collection of six deep-sea sediment cores (depths ranging from 257 to 3739 m) in the southern Gulf of Mexico. Sediment cores collected from the continental shelf and upper slope region of the Gulf of Mexico showed 240Pu/239Pu ratios of 0.15 to 0.26, and 239+240Pu-inventories ranging from 14.7 to 33.0 Bq m-2. Inventories and ratios are consistent with global fallout Pu for this tropical region. In contrast, sediment cores collected from the lower slope region and abyssal plain showed low 240Pu/239Pu ratios of 0.07 to 0.13 and much lower 239+240Pu inventories below 6.8 Bq m-2. This implies that only a small fraction of the expected global fallout Pu has reached the deep-sea sediments. The low 240Pu/239Pu isotope ratios indicate that fallout from the Nevada testing site was an important source of Pu in deep-sea sediments, and that this Pu was likely more efficiently scavenged from the water column than Pu from global fallout. We estimated that up to 44% of the total inventory of 239+240Pu in deep-sea sediments is due to the Nevada source. Low values and a progressive decrease of 240Pu/239Pu ratios and 239+240Pu inventories with increasing water depth have been previously reported for the Gulf of Mexico. Analysis of Pu isotopes in two sediment traps from the upper slope regions shows 240Pu/239Pu ratios comparable to those observed in global fallout. These results indicate that global fallout Pu is currently the main source of Pu in sinking particles in the water column. Therefore, a significant fraction of global fallout Pu must still be present, either in a dissolved phase, or as biologically recycled material in the water column, or scavenged on the shelf and shelf break. Our results bring to light important questions on the application of Pu isotopes to establish sediment chronologies in deep-sea sediments, since global fallout features such as the 1963 maximum are not available.

Mollusk death assemblages in 210Pb-dated marine sediment cores reveal recent biotic changes in the Gulf of Guanahacabibes, NW Cuba.

We investigated stratigraphic changes in mollusk death assemblages and geochemistry in sediment cores from four seagrass beds and one unvegetated site in the Gulf of Guanahacabibes (GG), NW Cuba. There was a transition from mangrove to seagrass beds, associated with sea level rise ∼6000 years ago. Sediment accumulation rates during the last century showed a general rise, but increased sharply after ∼1980, likely because of human activities. The GG displayed overall high mollusk γ-diversity, and our estimate of 189 species is biased toward the low end. High ß-diversity was driven by inter-site differences in grain size, vegetation cover, and nutrient input. Spatial heterogeneity within the basin influenced downcore abundance and diversity metrics, highlighting the influence of local drivers. Herbivorous gastropods dominated in seagrass beds and suspension feeder bivalves were dominant on sandy bottom. In the top parts of cores, species richness declined at two sites that were subject to high, human-mediated bulk sedimentation rates and eutrophication. Conservation measures are needed to preserve this hotspot of marine diversity.

Sedimentary record of the impact of management actions on pollution of Cartagena bay, Colombia.

The reconstruction of pollution in aquatic ecosystems is a useful tool to evaluate the effectiveness of management actions. Cartagena Bay (Colombia, Caribbean Sea) is one of the most impacted coastal zones in Colombia by a wide variety of human activities. A sediment core was dated using 210Pb and used to reconstruct the historical input of heavy metals, polycyclic aromatic hydrocarbons (PAHs), and organochlorinated pesticides to the bay. The highest pollutant concentrations were observed in the deeper core layers. The maximum mercury concentration (18.76 µg g-1) was observed at 61 cm depth, corresponding to 1967, when a chlor-alkali plant was operating. Since all pollutant concentrations have decreased due to better industrial management policies, their presence is a potential contamination risk through sediment remobilization and pollutant resuspension.

Calibration and use of well-type germanium detectors for low-level gamma-ray spectrometry of sediments using a semi-empirical method.

Gamma-ray spectrometry is a widely used technique to quantify the presence of numerous radionuclides in environmental samples. In this work, we describe a methodology for efficiency calibration of four well-type germanium detectors and their use for the determination of low-level activities of gamma emitters in sediment samples. An experimental efficiency calibration for each detector was built with three materials for 17 energies, ranging from 46.5 keV to 1460 keV. For efficiency transfer to different geometries and sample types, we used the effective solid angle approach (ET-Ω method). Final calibrations were calculated for all detectors, several counting geometries, and elemental composition of selected sample types. Calibrations were validated with six reference materials. This methodology allowed to reliably analyze nine gamma emitters (210Pb, 241Am, 234Th, 228Ac, 214Pb, 208Tl, 137Cs, 134Cs and 40K) in sediment samples. Using these calibrations, gamma emitter profiles of sediment cores from contrasting aquatic systems (lake, intertidal, marine and deep-sea areas) provided reliable profiles of 210Pb and artificial radionuclides useful for dating and stratigraphic interpretation. A protocol to implement this methodology is also presented.

210Pb-derived sediment accumulation rates across the Wider Caribbean Region.

The Wider Caribbean Region is an important tourist destination where agricultural, industrial and shipping activities are also carried on. Coastal zones are heavily populated and receive a high human pressure; however, few monitoring programmes allow assessing long-term anthropogenic impact trends in these areas, which are especially useful for integrated management programs. Through the support of the International Atomic Energy Agency (project RLA/7/012), sediment core activities of 210Pb and 137Cs were used to evaluate changes in sedimentation rates in 11 relevant coastal areas of the region, where environmental information is scarce, but needed to support national environmental policies. Most 210Pb activity profiles were atypical, attributed to non-steady sedimentation conditions; whereas 137Cs activity profiles, showing very low values, were of little help for 210Pb-dating corroboration. Results evidenced conspicuous changes in mass accumulation rates (MAR), specially through the Anthropocene (i.e. since ~1950s) in most cases, attributed to deforestation and land erosion (one of the clearest indicators of global change), and the input of urban and industrial untreated wastes. The recent MAR decrease in Havana Bay (Cuba) was attributed to the implementation of environmental policies, which showed that 210Pb-derived reconstruction of environmental changes is also useful to verify the effectiveness of management programs to control land-derived erosion and siltation issues. Since siltation can be detrimental to valuable coastal resources around the world, retrospective evaluations of sedimentation rates, based on 210Pb-dated cores, are highly recommended to assist integrated coastal zone management programs in the region and elsewhere.

Carbon and nitrogen isotopes to distinguish sources of sedimentary organic matter in a Caribbean estuary.

Carbon and nitrogen stable isotope compositions (δ13C and δ15N) of organic matter (OM) and total organic carbon to total nitrogen ratio (Corg/TN) in a sediment core collected in Sagua estuary (Cuba), were investigated to elucidate the origin of the Sedimentary OM (SOM) and changes in its main sources, over the last 100 years. Results showed almost constant values in the elemental and isotope composition of SOM from 1908 to 1970 with an abrupt change after 1970. From 1970 to 2005, δ13C increased from -21.2 up to -19.3 ‰, while δ15N declined from 1.5 to values close to 0 ‰. The output of the mass-balance model for the identification of OM sources indicated that δ13C and Corg/TN values are generally influenced by marine Particulate OM (POM) sources. Between 1900 and 1970, the main OM source in sediments was marine POM (>85 %), with freshwater POM contributing ca. 15%. Since 1970, the establishment of the Alacranes Dam determined drastic environmental changes influencing the OM sources in the area. Mixing models pointed to seagrasses (79 %) as the main contributors to SOM in the first period, while since 1973 onward, the contribution of human-derived sources such as fertilizers and urban discharges became greater. This information can provide baseline data for the environmental management of the Sagua watershed.

210Pb and 137Cs as tracers of recent sedimentary processes in two water reservoirs in Cuba.

Hanabanilla and Paso Bonito Reservoirs are the main fresh water sources for about half a million inhabitants in central Cuba. Prior to this investigation precise information about the losses of storage capacity was not available. Sedimentation is the dominant process leading to reduction in water storage capacity. We investigated the sedimentation process in both reservoirs by analyzing environmental radionuclides (e.g. 210Pb, 226Ra and 137Cs) in sediment cores. In the shallow Paso Bonito Reservoir (mean depth of 6.5 m; water volume of 8 × 106 m3), we estimated a mean mass accumulation rate (MAR) of 0.4 ± 0.1 g cm-2y-1 based on 210Pb chronologies. 137Cs was detected in the sediments, but due to the recent construction of this reservoir (1975), it was not possible to use it to validate the 210Pb chronologies. The estimated MAR in this reservoir is higher than the typical values reported in similar shallow fresh water reservoirs worldwide. Our results highlight a significant loss of water storage capacity during the past 30 years. In the deeper and larger Hanabanilla Reservoir (mean depth of 15.5 m; water volume of 292 × 106 m3), the MAR was investigated in three different sites of the reservoir. The mean MARs based on the 210Pb chronologies varied between 0.15 and 0.24 g cm-2y-1. The MARs calculated based on the 137Cs profiles further validated these values. We show that the sediment accumulation did not change significantly over the last 50 years. A simple empirical mixing and sedimentation model that assumes 137Cs in the water originated from both, direct atmospheric fallout and the catchment area, was applied to interpret the 137Cs depth profiles. The model consistently reproduced the measured 137Cs profiles in the three cores (R2 > 0.9). Mean residence times for 137Cs in the water and in the catchment area of 1 y and 35-50 y, respectively were estimated. The model identified areas where the catchment component was higher, zones with higher erosion in the catchment, and sites where the fallout component was quantitatively recorded in the sediments.

Radiocronología de sedimentos marinos y su aplicación en la comprensión de los procesos de contaminación ambiental en ecosistemas marinos cubanos / Radiochronology of marine sediments and its application to the knowledge of the process of environmental pollution in coastal Cuban ecosystems

En este trabajo se sistematizan algunos resultados alcanzados en la aplicación de la radiocronología de sedimentos marinos para la reconstrucción de bases de datos y el conocimiento de la evolución de la contaminación ambiental en cuatro ecosistemas costeros de relevancia nacional: las bahías de Cienfuegos y la Habana, así como los estuarios de los ríos Sagua y La Coloma en el Golfo de Batabanó. Se seleccionaron flujos de metales pesados y compuestos orgánicos persistentes que fueron discutidos para estos ecosistemas. Se mostró la eficacia de la radiocronología como herramienta para la gestión ambiental y el conocimiento de los procesos temporales de contaminación en el medio acuático

The results achieved in the implementation of the radiochronology of marine sediments for the reconstruction of databases and knowledge of the evolution of environmental pollution in four coastal ecosystems of national significance are presented in this paper Fluxes of selected heavy metals and persistent organic compounds are discussed for the Cienfuegos and Havana bays and Sagua and La Coloma estuaries. Finally, is showed the effectiveness of radiochronology of sediments as a useful tool for environmental management and knowledge of temporal processes of pollution in the aquatic environment

One-century decline of mollusk diversity as consequence of accumulative anthropogenic disturbance in a tropical estuary (Cuban Archipelago).

In order to infer changes in sediments and mollusk assemblages for the last century, we used biogeochemical data from two 210Pb dated cores collected in Sagua La Grande estuary, Cuban Archipelago. We found evidences of cumulative anthropogenic disturbance during the last century, causing considerable depletion of mollusk assemblage diversity and enhancement of the dominance of deposit feeding species. The sequence of impacts assessed was i) eutrophication due to nutrient releases from urban settlements, ii) habitat alteration due to water channeling and damming, and iii) mercury pollution. These successive impacts caused a steady diversity depletion from ca. 70 mollusk species in 1900 to less than five in 2010. Only two species persisted in the estuary: Nuculana acuta and Finella dubia. Hurricanes did not impact the molluscan fauna in the long term. The effects of the anthropogenic impacts suggest that the resilience of this estuarine system is compromised.

Mercury contamination of riverine sediments in the vicinity of a mercury cell chlor-alkali plant in Sagua River, Cuba.

Sediment is a great indicator for assessing coastal mercury contamination. The objective of this study was to assess the magnitude of mercury pollution in the sediments of the Sagua River, Cuba, where a mercury-cell chlor-alkali plant has operated since the beginning of the 1980s. Surface sediments and a sediment core were collected in the Sagua River and analyzed for mercury using an Advanced Mercury Analyser (LECO AMA-254). Total mercury concentrations ranged from 0.165 to 97 µg g(-1) dry weight surface sediments. Enrichment Factor (EF), Index of Geoaccumulation (Igeo) and Sediment Quality Guidelines were applied to calculate the degrees of sediment contamination. The EF showed the significant role of anthropogenic mercury inputs in sediments of the Sagua River. The result also determined that in all stations downstream from the chlor-alkali plant effluents, the mercury concentrations in the sediments were higher than the Probable Effect Levels value, indicating a high potential for adverse biological effects. The Igeo index indicated that the sediments in the Sagua River are evaluated as heavily polluted to extremely contaminated and should be remediated as a hazardous material. This study could provide the latest benchmark of mercury pollution and prove beneficial to future pollution studies in relation to monitoring works in sediments from tropical rivers and estuaries.

Observations of fallout from the Fukushima reactor accident in Cienfuegos, Cuba.

Following the recent accident at the Fukushima Daiichi nuclear power plant in Japan, radioactive contamination was observed near the reactor site. As a contribution towards the understanding of the worldwide impact of the accident, we collected fallout samples in Cienfuegos, Cuba, and examined them for the presence of above normal amounts of radioactivity. Gamma ray spectra measured from these samples showed clear evidence of fission products (131)I and (137)Cs. However, the fallout levels measured for these isotopes (135 ± 4.78 mBq m(-2) day(-1) for (131)I and 10.7 ± 0.38 mBq m(-2) day(-1)for (137)Cs) were very low and posed no health risk to the public. The doses received as consequence to the Fukushima fallout by the Cienfuegos population's (0.002 mSv per year) don't overcome the limit of dose (1 mSv per year) fixed for the public in Cuba.

Historical changes of sediments and mollusk assemblages in the Gulf of Batabanó (Caribbean Sea) in the twentieth century.

The first paleoecological reconstruction of the biogeochemical conditions of the Gulf of Batabanó, Caribbean Sea was performed from (210)Pb-dated sediment cores. Depth profiles of 20 major elements and trace metals, organic compounds, grain size, and mollusk assemblage composition were determined from 9 stations encompassing unconsolidated sediments in the gulf. Spatial heterogeneity was evident for the geochemistry of sediments and for the mollusk assemblage composition. Our reconstruction indicates that pollution is not a critical threat to the ecosystem, although a slight historical increase of lead enrichment factor was detected probably due to long-range atmospheric fallout. Mollusk assemblages were composed by 168 species belonging to 59 families and no temporal trends in the species diversity or assemblage composition were detected, suggesting no depletion of diversity or habitat loss. Other signals of habitat loss such as changes in organic budget or increase of fine sediment fraction were absent or weak. Nitrogen retained in sediments changed by <1% in the century, indicating no historical events of eutrophication or oligotrophication in the gulf. Historical decrease of fine sediment fraction in the eastern sector would be linked to modifications in sedimentation rate, land use, and/or particle transport from the shelf border; this also suggests that both sectors have different sedimentary dynamics. Although, on theoretical grounds, historical fishery may have caused deleterious ecosystem effects by overexploitation of spiny lobster stocks, no evidence of habitat degradation or loss, caused by fisheries, could be detected.

Chemical speciation of arsenic in different marine organisms: Importance in monitoring studies.

Arsenic is a widely distributed element in the marine environment. Inorganic and organic compounds have extremely different toxicological effects, and their characterization is thus of great utility when monitoring and assessing the impact of arsenic pollution. In this study both the levels of total arsenic and its chemical speciation were analyzed in several marine organisms collected from Cienfuegos Bay (Cuba) following an episode of acute As-contamination. Fish from the more impacted site were characterized by elevated concentrations of arsenic (up to 500 microg/g d.w.) and inorganic species represented the predominant forms in muscle tissues of these organisms.