Regional assessment of the historical trends of mercury in sediment cores from Wider Caribbean coastal environments.

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.

Establishing a Receptor Binding Assay for Ciguatoxins: Challenges, Assay Performance and Application.

Ciguatera, a global issue, lacks adequate capacity for ciguatoxin analysis in most affected countries. The Caribbean region, known for its endemic ciguatera and being home to a majority of the global small island developing states, particularly needs established methods for ciguatoxin detection in seafood and the environment. The radioligand receptor binding assay (r-RBA) is among the in vitro bioassays currently used for ciguatoxin analysis; however, similarly to the other chemical-based or bioassays that have been developed, it faces challenges due to limited standards and interlaboratory comparisons. This work presents a single laboratory validation of an r-RBA developed in a Cuban laboratory while characterizing the performance of the liquid scintillation counter instrument as a key external parameter. The results obtained show the assay is precise, accurate and robust, confirming its potential as a routine screening method for the detection and quantification of ciguatoxins. The new method will aid in identifying high-risk ciguatoxic fish in Cuba and the Caribbean region, supporting monitoring and scientific management of ciguatera and the development of early warning systems to enhance food safety and food security, and promote fair trade fisheries.

Variation of 210-polonium in the cephalopod community from the Bay of Biscay, North-East Atlantic.

Among natural radionuclides, 210Po is the major contributor to the radiation dose received by marine organisms. In cephalopods, 210Po is concentrated in the digestive gland, which contains over 90% of the whole-body burden of the nuclide. Although previous studies showed that 210Po was taken up independently of 210Pb, its parent nuclide, very little is known about the factors influencing its levels in cephalopods. To the best of our knowledge, no studies investigated 210Po levels in different species at the same time. In the present study, 210Po was analysed in the digestive gland of 62 individuals from 11 species representing a large range of feeding ecologies and habitats, including squids, cuttlefish and octopus species from coastal to deep-oceanic habitats. Among species, the highest activity was measured in Loligo vulgaris (5720 ± 3606 Bq/kg) and the lowest in T. megalops (188 Bq/kg). However, considering the habitats (benthic vs pelagic and neritic vs oceanic), no significant differences appeared. At the species level, no differences between sexes were found so both sexes were plotted together to test the size effect for species with at least 8 individuals (i.e., Eledone cirrhosa, L. vulgaris, L. forbesi and Sepia officinalis). In the first three species, 210Po levels decreased significantly with increasing size or weight but not in S. officinalis. In squid, this could be related to ontogenetic changes in diet from a high proportion of crustaceans (high Po content) in small individuals to fish (low Po content) in larger individuals, while the high dietary plasticity of S. officinalis at all stages of its life cycle could explain the lack of decrease in 210Po with size. In comparison to the few data from the literature, the levels of 210Po concentrations in the cephalopod community of the Bay of Biscay were overall in the same range than those reported in other cephalopods, varying across 4 orders of magnitude. Further studies are needed to understand the mechanism of retention in the cephalopod digestive gland.

Microplastic-sorbed persistent organic pollutants in coastal Mediterranean Sea areas of Tunisia.

Microplastics (MPs) are emerging pollutants of global concern due to their pervasiveness, high sorption ability for persistent organic pollutants (POPs) and direct and indirect toxicity to marine organisms, ecosystems, as well as humans. As one of the major coastal interfaces, beaches are considered among the most affected ecosystems by MPs pollution. The morphological characteristics of MPs (pellets and fragments) collected from four beaches along the Tunisian coast and sorbed POPs, including polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs), were investigated in this study. The results showed that the MPs varied greatly in color, polymer composition and degradation degree. The color varied from colored to transparent and the most prevalent polymer identified using Raman spectroscopy was polyethylene. Scanning electron microscope (SEM) images exhibited various surface degradation features including cavities, cracks, attached diatom remains, etc. The concentrations of Σ12PCBs over all beaches ranged from 14 to 632 ng g-1 and 26 to 112 ng g-1 in the pellets and fragments, respectively, with a notable presence and dominance of highly-chlorinated PCBs such as CB-153 and -138. Among the OCPs, γ-HCH is the only compound detected with concentrations ranging from 0.4 to 9.7 ng g-1 and 0.7 to 4.2 ng g-1 in the pellets and fragments, respectively. Our findings indicate that MPs found on the Tunisian coast may pose a chemical risk to marine organisms as the concentrations of PCBs and γ-HCH in most of the analysed samples exceeded the sediment-quality guidelines (SQG), especially the effects range medium (ERM) and the probable effects level (PEL). As the first report of its kind, the information gathered in this study can serve as the baseline and starting point for future monitoring work for Tunisia and neighbouring countries, as well as for stakeholders and coastal managers in decision-making processes.

Trends of legacy and emerging organic contaminants in a sediment core from Cienfuegos Bay, Cuba, from 1990 to 2015.

Legacy and emerging organic pollutants pose an ever-expanding challenge for the marine environment. This study analysed a dated sediment core from Cienfuegos Bay, Cuba, to assess the occurrence of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), alternative halogenated flame retardants (aHFRs), organophosphate esters (OPEs), and phthalates (PAEs) from 1990 to 2015. The results evidence the continuing presence of historical regulated contaminants (PCBs, OCPs, and PBDEs) in the southern basin of Cienfuegos Bay. PCB contamination declined since 2007, likely in response to the gradual global phasing out of PCB containing materials. There have been relatively consistent low accumulation rates for OCPs and PBDEs at this location (in 2015 approximately 1.9 and 0.26ng/cm2/year, respectively, with 2.8ng/cm2/year for Σ6PCBs), with indications of recent local DDT use in response to public health emergencies. In contrast, sharp increases are observed between 2012 and 2015 for the contaminants of emerging concern (PAEs, OPEs, and aHFRs), and in the case of two PAEs (DEHP and DnBP) the concentrations were above the established environmental effect limits for sediment dwelling organisms. These increasing trends reflect the growing global usage of both alternative flame retardants and plasticizer additives. Local drivers for these trends include nearby industrial sources such as a plastic recycling plant, multiple urban waste outfalls, and a cement factory. The limited capacity for solid waste management may also contribute to the high concentrations of emerging contaminants, especially plastic additives. For the most recent year (2015), the accumulation rates for Σ17aHFRs, Σ19PAEs, and Σ17OPEs into sediment at this location were estimated to be 10, 46 000, and 750ng/cm2/year, respectively. This data provides an initial survey of emerging organic contaminants within this understudied region of the world. The increasing temporal trends observed for aHFRs, OPEs, and PAEs highlights the need for further research concerning the rapid influx of these emerging contaminants.

Summer bloom of Vulcanodinium rugosum in Cienfuegos Bay (Cuba) associated to dermatitis in swimmers.

The marine dinoflagellate Vulcanodinium rugosum produces powerful paralyzing and cytotoxic compounds named pinnatoxins (PnTX) and portimines. Even though, no related human intoxication episodes following direct exposure in seawater or the ingestion of contaminated seafood have been documented so far. This study aimed at investigating a dinoflagellate bloom linked to acute dermatitis cases in two recreational beaches in Cienfuegos Bay, Cuba. We used epidemiological and clinical data from 60 dermatitis cases consisting of individuals in close contact with the bloom. Seawater physical-chemical properties were described, and the microorganism causing the bloom was identified by means of light and scanning electron microscopy. Morphological identification was confirmed genetically by sequencing the internal transcribed spacers ITS1 and ITS2, and the 5.8S rDNA region. Toxic compounds were identified from a bloom extract using liquid chromatography (LC) coupled to high-resolution mass spectrometry (HRMS), and their concentrations were estimated based on low-resolution tandem mass spectrometry (LC-MS/MS). Sixty people who had prolonged contact with the dinoflagellate bloom suffered acute dermal irritation. Most patients (79.2%) were children and had to be treated with antibiotics; some required >5-day hospitalization. Combined morphological and genetic characters indicated V. rugosum as the causative agent of the bloom. rDNA sequences of the V. rugosum genotype found in the bloom aligned with others from Asia, including material found in the ballast tank of a ship in Florida. The predominant toxins in the bloom were portimine, PnTX-F and PnTX-E, similar to strains originating from the Pacific Ocean. This bloom was associated with unusual weather conditions such as frequent and prolonged droughts. Our findings indicate a close link between the V. rugosum bloom and a dermatitis outbreak among swimmers in Cienfuegos Bay. Phylogenetic evidence suggests a recent introduction of V. rugosum from the Pacific Ocean into Caribbean waters, possibly via ballast water.

Ciguatoxin Occurrence in Food-Web Components of a Cuban Coral Reef Ecosystem: Risk-Assessment Implications.

In Cuba, ciguatera poisoning associated with fish consumption is the most commonly occurring non-bacterial seafood-borne illness. Risk management through fish market regulation has existed in Cuba for decades and consists of bans on selected species above a certain weight; however, the actual occurrence of ciguatoxins (CTXs) in seafood has never been verified. From this food safety risk management perspective, a study site locally known to be at risk for ciguatera was selected. Analysis of the epiphytic dinoflagellate community identified the microalga Gambierdiscus. Gambierdiscus species included six of the seven species known to be present in Cuba (G. caribaeus, G. belizeanus, G. carpenteri, G. carolinianus, G. silvae, and F. ruetzleri). CTX-like activity in invertebrates, herbivorous and carnivorous fishes were analyzed with a radioligand receptor-binding assay and, for selected samples, with the N2A cell cytotoxicity assay. CTX activity was found in 80% of the organisms sampled, with toxin values ranging from 2 to 8 ng CTX3C equivalents g-1 tissue. Data analysis further confirmed CTXs trophic magnification. This study constitutes the first finding of CTX-like activity in marine organisms in Cuba and in herbivorous fish in the Caribbean. Elucidating the structure-activity relationship and toxicology of CTX from the Caribbean is needed before conclusions may be drawn about risk exposure in Cuba and the wider Caribbean.

Deciphering key processes controlling rainfall isotopic variability during extreme tropical cyclones.

The Mesoamerican and Caribbean (MAC) region is characterized by tropical cyclones (TCs), strong El Niño-Southern Oscillation events, and climate variability that bring unique hazards to socio-ecological systems. Here we report the first characterization of the isotopic evolution of a TC (Hurricane Otto, 2016) in the MAC region. We use long-term daily rainfall isotopes from Costa Rica and event-based sampling of Hurricanes Irma and Maria (2017), to underpin the dynamical drivers of TC isotope ratios. During Hurricane Otto, rainfall exhibited a large isotopic range, comparable to the annual isotopic cycle. As Hurricane Otto organized into a Category 3, rapid isotopic depletion coupled with a decrease in d-excess indicates efficient isotopic fractionation within ~200 km SW of the warm core. Our results shed light on key processes governing rainfall isotope ratios in the MAC region during continental and maritime TC tracks, with applications to the interpretation of paleo-hydroclimate across the tropics.

A radioligand receptor binding assay for ciguatoxin monitoring in environmental samples: Method development and determination of quality control criteria.

Ciguatoxins are algal toxins responsible for tens of thousands of human intoxications yearly, both in tropical and subtropical endemic regions as well as worldwide through fish exportation. Previously developed methods for biotoxin surveillance in the environment and seafood include analytical methods and in vivo and in vitro bioassays. The radioligand receptor binding assay (r-RBA) is among the in vitro methodologies currently used for the detection and quantification of marine biotoxins. For the ciguatoxin group, the r-RBA has been widely used as a means to characterize the mode of action and as detection method in various biological matrices. Yet, screening methods have not been standardized, and the details of the ciguatoxin-specific r-RBA are not well-documented, which limit interlaboratory comparison and progress toward method validation. This work presents the development of an optimized r-RBA for ciguatoxins and provides guidance on its use and quality control checks for analysis of environmental samples. We focus on the analysis of critical parameters involved in determining assay acceptability. Calculation of toxin concentrations in fish samples is illustrated with four examples. Thus, this paper provides the detailed information required for a full validation of the r-RBA, a necessary step toward the development and implementation of a regulatory monitoring programme for ciguatoxins in seafood products using the r-RBA.

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

Monte Carlo simulation of the efficiency response of a well-type HPGe detector at 46.54 keV / Simulación por Monte Carlo de la respuesta en eficiencia de un detector HPGe tipo pozo a la energía de 46.54 keV

In this paper, we used the Monte Carlo simulations method in a well-type HPGe detector using directly the manufacturer supplied data in order to simulate the effi ciency response at 46.54 keV. The efficiency values were calculated as a function of the fi lling height of the sample into the measurement geometry and results were found in good agreement with experimental data. The main deviations were less than 2.5 % with a mean of 0.9 %, which is totally satisfactory for the purposes of environmental samples measurements. We also present a brief discussion about the response of the detector to different values of its geometric parameters.

En el trabajo se utilizaron los métodos de simulación por Monte Carlo en un detector HPGe tipo pozo, usando directamente los parámetros del fabricante para simular la respuesta en eficiencia a la energía de 46.54 keV. Los valores de efi ciencia se calcularon en función de la altura de la muestra en la geometría de medición y los resultados se correspondieron con los valores experimentales. Las mayores diferencias fueron menores que el 2.5 % con un promedio de 0.9 %, lo que es totalmente satisfactorio para la medición de muestras ambientales. Se presentó una breve discusión sobre la respuesta del detector para diferentes parámetros geométrico.

Application of the Monte Carlo efficiency transfer method to an HPGe detector with the purpose of environmental samples measurement.

Monte Carlo efficiency transfer method was used to determine the full energy peak efficiency of a coaxial n-type HPGe detector. The efficiencies calibration curves for three Certificate Reference Materials were determined by efficiency transfer using a (152)Eu reference source. The efficiency values obtained after efficiency transfer were used to calculate the activity concentration of the radionuclides detected in the three materials, which were measured in a low-background gamma spectrometry system. Reported and calculated activity concentration show a good agreement with mean deviations of 5%, which is satisfactory for environmental samples measurement.

Atmospheric deposition patterns of (210)Pb and (7)Be in Cienfuegos, Cuba.

The radiometric composition of bulk deposition samples, collected monthly for one year, February 2010 until January 2011, at a site located in Cienfuegos (22° 03' N, 80° 29' W) (Cuba), are analysed in this paper. Measurement of (7)Be and (210)Pb activity concentrations were carried out in 12 bulk deposition samples. The atmospheric deposition fluxes of (7)Be and (210)Pb are in the range of 13.2-132 and 1.24-8.29 Bq m(-2), and their mean values are: 56.6 and 3.97 Bq m(-2), respectively. The time variations of the different radionuclide have been discussed in relation with meteorological factors and the mean values have been compared to those published in recent literature from other sites located at different latitudes. The annual average flux of (210)Pb and (7)Be were 47 and 700 Bq m(-2) y(-1), respectively. Observed seasonal variations of deposition data are explained in terms of different environmental features. The atmospheric deposition fluxes of (7)Be and (210)Pb were moderately well correlated with precipitation and well correlated with one another. The (210)Pb/(7)Be ratios in the monthly depositions samples varied in the range of 0.05-0.10 and showed a strong correlation with the number of rainy days.

Niveles de radionúclidos naturales y metales pesados en suelos urbanos de la ciudad de Cienfuegos, Cuba / Heavy metal and natural radionuclide levels in urban soils from Cienfuegos city, Cuba

Se determinan las concentraciones de metales pesados y radionúclidos naturales en suelos superficiales (0-10 cm) de la ciudad de Cienfuegos, Cuba, mediante las técnicas de fluorescencia de rayos X y espectrometría gamma respectivamente. Los resultados de la medición de metales pesados mostraron que las concentraciones promedio de Ni, Cu, Zn y Pb en los suelos estudiados son superiores a los valores correspondientes de fondo. El cálculo del Índice de Polución Integral permitió determinar que estos suelos presentan una contaminación severa por metales pesados. Las concentraciones de , y en los suelos urbanos de Cienfuegos se encuentran en los intervalos de 8.3-32.7, 3.7-10.7 y 129-356 , con promedios de 22.6, 6.3 y 272 respectivamente, valores que son similares a los reportados para la zona Centro-Sur de Cuba. La tasa de dosis absorbida en aire y la dosis equivalente efectiva anual que recibe la población local producto de la radiación natural es inferior a los límites establecidos internacionalmente. Se determinaron correlaciones positivas significativas de -Cu y -Zn, indicando la posible presencia de una fuente de contaminación por estos elementos en la zona.

Concentrations of heavy metals and natural radionuclides in topsoil (0-10cm) from Cienfuegos city, Cuba, were determined by using X-ray fluorescence analysis and gamma ray spectrometry, respectively. The measured results of heavy metals show that the mean concentrations of Ni, Cu, Zn and Pb in the studied soil samples are higher than their corresponding background values. The calculated results of integrated pollution index of heavy metals indicate that the studied soils present severely heavy metal contamination. The concentrations of , and in the studied soil samples range from 8.3 to 32.7, 3.7 to 10.7 and 129 to 356 with an average of 22.6, 6.3 and 272 , respectively, which are similar than the average concentrations reported for South-central Cuban soils. The air absorbed dose rate and the annual effective dose equivalent received by the local residents due to the natural radionuclides in soil are lesser than the worldwide established limits. A significantly positive -Cu and -Zn correlations were determined, indicating the possible existence of a source of pollution due to the presence of these elements in the area.

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.

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.