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.

Extruded polystyrene microplastics as a source of brominated flame retardant additives in the marine environment: long-term field and laboratory experiments.

Microplastics (MPs) in the environment have become a global concern, not only for the physical effects of the plastic particles themselves but also for being vectors of chemical additives. In this context, little is known about the ability of MPs, particularly extruded polystyrene microplastics (XPS-MPs), to release organic chemical additives in the marine environment. In this study, a series of field and laboratory experiments were carried out to determine the leaching behaviour of organic additives including brominated flame retardants from XPS-MPs into seawater. The conducted experiments confirmed a rapid release of bisphenol A (BPA), 2,4,6-tribromophenol (TBP), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane diastereoisomers (α-, ß-, and γ-HBCDD) from the studied MPs followed by a slower rate of release over time. The effects of environmental factors on the leaching rates of these additives were also examined. Increasing Dissolved Organic Matter (DOM) concentrations and the temperature of the seawater enhanced the release of additives by increasing their solubility and polymer flexibility. In contrast, pH tested at 7, 7.5 and 8 was found to have a minor effect on additives leaching; and salinity negatively affected the leaching rate likely due to their reduced solubility and reduced diffusion from the MPs. The present study provides empirical evidence of the behaviour of XPS-MPs as a source of organic additives in the marine environment that merit further investigation.

Survey of legacy and emerging per- and polyfluorinated alkyl substances in Mediterranean seafood from a North African ecosystem.

Despite the ubiquity of per- and polyfluorinated alkyl substances (PFAS) in all environmental compartments, little is known about the pollution they cause on the African continent, neither on levels, nor effects. Here we examined the occurrence and levels of 21 legacy and emerging PFAS in 9 marine species (3 fish, 2 crustaceans and 4 mollusks) collected from Bizerte lagoon, Northern Tunisia. Furthermore, assessment of potential human health risks through consumption of contaminated seafood was examined. This is the first study assessing PFAS in Mediterranean coastal areas of North Africa. Twelve out of the 21 targeted PFAS were detected, evidencing the occurrence of PFAS in seafood from North Africa, albeit at low levels. The Æ©21PFAS concentrations in all seafood samples ranged from 0.202 ng g-1 dry weight (dw) to 2.89 ng g-1 dw, with a mean value of 1.10 ± 0.89 ng g-1 dw. The profiles of PFAS varied significantly among different species, which might be related to their different trophic level, protein content, feeding behaviour and metabolism. Generally, current exposure to PFAS through seafood consumption indicates that it should not be of concern to the local consumers, at least for those PFAS for which information is available.

A review on per- and polyfluorinated alkyl substances (PFASs) in microplastic and food-contact materials.

Plastic, paper and cardboard are widely used as food contact materials (FCMs), due to its numerous favourable characteristics. However, they are usually coated with hazardous substances, such as per- and polyfluorinated alkyl substances (PFASs). PFASs, with its functional properties of oil- and water-repellency, can migrate from FCMs into the food and cause potential risk to human health. There are also increasing concerns about the harm that FCMs can cause to the environment. These concerns include accumulation of non-degradable plastics in the environment, generation of microplastics (MPs) and nanoplastics, and release of PFASs from FCMs. While many reviews have been conducted on PFASs in the environment, including their occurrence, fate, toxicity, biodegradation, migration in ecosystems and remediation technologies, a systematic review of PFASs in FCMs and MPs is currently lacking. In addition, our knowledge of the PFAS sorption processes on MPs is rather limited, and in particular their desorption processes. Thus, this review aims to (1) review the presence of various classes of PFASs in FCMs and their migration into food, (2) review the PFASs in MPs and summarize the sorption mechanisms, and factors that influence their sorption behaviour on MPs in the aquatic environment, and (3) identify the current research gaps and future research directions to predict the risks associated with the presence and sorption of PFASs in FCMs and MPs.

A comprehensive evaluation of two sample treatment procedures for the determination of emerging and historical halogenated flame retardants in biota.

Two different sample preparation protocols for the determination of 37 emerging and historical halogenated flame retardants (HFRs) in marine tissues were compared with regards to extraction recovery, lipid removal efficiency, repeatability, reproducibility, and ability to measure sub-ng g-1 (dry weight) concentrations in marine biota. One method involved a purification step using gel permeation chromatography (GPC) followed by a HPLC fractionation step on a Partisil amino-cyano normal phase (GPC-Partisil procedure) and the other more traditional method was based on sulphuric acid treatment followed by silica column fractionation (H2SO4-silica procedure). The samples were analysed by gas chromatography (GC) and liquid chromatography (LC) tandem mass spectrometry (MS/MS). Sample fractionation in both methods enabled unique sample preparation procedures to isolate the GC from the LC amenable compounds. Both methods could remove > 99% of the lipids which was necessary prior to GC- and LC-MS/MS analyses. The majority of the target compounds (70%) had acceptable recoveries between 60-120% for both methods. However, the sulphuric acid treatment resulted in the degradation of the TBP-AE and the silica column fractionation resulted in the loss of BEH-TEBP and the elution of PBB-Acr and TBBPA-BME in the unsuitable fraction. High recoveries of DBE-DBCH (α+ß), EHTBB, BTBPE, BEH-TEBP, and PBB-Acr were attributed to matrix effects, suggesting the need to use isotope-labelled surrogate standards of the target compounds. The optimisation of the silica column chromatography, GPC, and Partisil fractionation is described and discussed to afford easy implementation of the method. The method using GPC followed by Partisil fractionation is more efficient and more reproducible than the sulphuric acid-silica procedure. The application of this method to marine biota reference materials revealed the presence of relatively high concentrations of DBE-DBCH isomers and BDE-47 in fish samples. The method detection limits comply with the recommendations of the European Commission.

Leaching of flame-retardants from polystyrene debris: Bioaccumulation and potential effects on coral.

Marine plastic debris can act as a reservoir of chemical additives that can pose a potential threat to sensitive ecosystems such as coral reefs. A survey of foam macrodebris collected on beaches indeed revealed high concentrations of hexabromocyclododecanes (ΣHBCDD) in polystyrene (PS) samples (up to 1940 µg g-1). Results also showed that PS fragments can still leach over 150 ng g-1 d-1 of ΣHBCDD (primarily as the α-isomer) for relatively long durations, and that these additives are readily bioaccumulated and well-retained by corals. Despite significant HBCDD bioaccumulation in coral tissue, short-term exposure to HBCDD or PS leachate had no considerable effect on coral photosynthetic activity, symbiont concentration and chlorophyll content. Exposure to the PS leachate did however cause consistent polyp retraction in nubbins over the 5-day exposure. This response was not observed in animals exposed to HBCDD alone, suggesting that another constituent of the leachate stressed corals.

A new marine sediment certified reference material (CRM) for the determination of persistent organic contaminants: IAEA-459.

A new marine sediment certified reference material (IAEA 459) with very low concentrations (µg kg-1) for a variety of persistent organic contaminants (POPs) listed by the Stockholm Convention, as well as other POPs and priority substances (PSs) listed in many environmental monitoring programs was developed by the IAEA. The sediment material was collected from the Ham River estuary in South Korea, and the assigned final values were derived from robust statistics on the results provided by selected laboratories which demonstrated technical and quality competence, following the guidance given in ISO Guide 35. The robust mean of the laboratory means was assigned as certified values, for those compounds where the assigned value was derived from at least five datasets and its relative expanded uncertainty was less than 40% of the assigned value (most of the values ranging from 8 to 20%). All the datasets were derived from at least two different analytical techniques which have allowed the assignment of certified concentrations for 22 polychlorinated biphenyl (PCB) congeners, 6 organochlorinated (OC) pesticides, 5 polybrominated diphenyl ethers (PBDEs), and 18 polycyclic aromatic hydrocarbon (PAHs). Mass fractions of compounds that did not fulfill the criteria of certification are considered information values, which include 29 PAHs, 11 PCBs, 16 OC pesticides, and 5 PBDEs. The extensive characterization and associated uncertainties at concentration levels close to the marine sediment quality guidelines will make CRM 459 a valuable matrix reference material for use in marine environmental monitoring programs.

Application of nuclear techniques to environmental plastics research.

Plastic pollution is ubiquitous in aquatic environments and its potential impacts to wildlife and humans present a growing global concern. Despite recent efforts in understanding environmental impacts associated with plastic pollution, considerable uncertainties still exist regarding the true risks of nano- and micro-sized plastics (<5 mm). The challenges faced in this field largely relate to the methodological and analytical limitations associated with studying plastic debris at low (environmentally relevant) concentrations. The present paper highlights how radiotracing techniques that are commonly applied to trace the fate and behaviour of chemicals and particles in various systems, can contribute towards addressing several important and outstanding questions in environmental plastic pollution research. Specifically, we discuss the use of radiolabeled microplastics and/or chemicals for 1) determining sorption/desorption kinetics of a range of contaminants to different types of plastics under varying conditions, 2) understanding the influence of microplastics on contaminant and nutrient bioaccumulation in aquatic organisms, and 3) assessing biokinetics, biodistribution, trophic transfer and potential biological impacts of microplastic at realistic concentrations. Radiotracer techniques are uniquely suited for this research because of their sensitivity, accuracy and capacity to measure relevant parameters over time. Obtaining precise and timely information on the fate of plastic particles and co-contaminants in wildlife has widespread applications towards effective monitoring programmes and environmental management strategies.

Comprehensive analytical methodology to determine hydrocarbons in marine waters using extraction disks coupled to glass fiber filters and compound-specific isotope analyses.

Solid-phase extraction of both aliphatic (AHs) and aromatic polycyclic hydrocarbons (PAHs) from seawater samples was evaluated using a GFF filter stacked upon an octadecyl bonded silica (C18) disk. Stable-isotope measurements were developed on hydrocarbons extracted from both GFF and C18-disks in order to characterize the source of hydrocarbons. A clear partition of hydrocarbon compounds between the dissolved and the particulate phase was highlighted. PAHs showed a higher affinity with the dissolved phase (recoveries efficiency of 48-71%) whereas AHs presented strong affinity with the particulate phase (up to 76% of extraction efficiency). Medium volumes of seawater samples were tested and no breakthrough was observed for a 5L sample. Isotopic fractionation was investigated within all analytical steps but none was evidenced. This method has been applied to harbor seawater samples and very low AH and PAH concentrations were achieved. Due to the low concentration levels of hydrocarbons in the samples, the source of hydrocarbons was determined by molecular indices rather than isotopic measurements and a pyrolytic origin was evidenced. The aliphatic profile also revealed the presence of long-chain linear alkylbenzenes (LABs). The methodology presented here would better fit to polluted coastal environments affected by recent oil spills.

Bacterial carbon dependence on freshly produced phytoplankton exudates under different nutrient availability and grazing pressure conditions in coastal marine waters.

The effects of grazing pressure and inorganic nutrient availability on the direct carbon transfer from freshly produced phytoplankton exudates to heterotrophic bacteria biomass production were studied in Mediterranean coastal waters. The short-term incorporation of ¹³C (H¹³CO3) in phytoplankton and bacterial lipid biomarkers was measured as well as the total bacterial carbon production (BP), viral lysis and the microbial community structure under three experimental conditions: (1) High inorganic Nutrient and High Grazing (HN + HG), (2) High inorganic Nutrient and Low Grazing (HN + LG) and (3) under natural in situ conditions with Low inorganic Nutrient and High Grazing (LN + HG) during spring. Under phytoplankton bloom conditions (HN + LG), the bacterial use of freshly produced phytoplankton exudates as a source of carbon, estimated from ¹³C enrichment of bacterial lipids, contributed more than half of the total bacterial production. However, under conditions of high grazing pressure on phytoplankton with or without the addition of inorganic nutrients (HN + HG and LN + HG), the ¹³C enrichment of bacterial lipids was low compared with the high total bacterial production. BP therefore seems to depend mainly on freshly produced phytoplankton exudates during the early phase of phytoplankton bloom period. However, BP seems mainly relying on recycled carbon from viral lysis and predators under high grazing pressure.

Distribution of petroleum hydrocarbons and organochlorinated contaminants in marine biota and coastal sediments from the ROPME Sea Area during 2005.

The composition and spatial distribution of various petroleum hydrocarbons (PHs), comprising both aliphatic and polycyclic aromatic hydrocarbons (PAHs), and selected chlorinated pesticides and PCBs were measured in biota and coastal sediments from seven countries in the Persian Gulf and the Gulf of Oman (Bahrain, Iran, Kuwait, Oman, Qatar, Saudi Arabia and the United Arab Emirates). Evidence of extensive marine contamination with respect to organochlorinated compounds and PHs was not observed. Only one site, namely the BAPCO oil refinery in Bahrain, was considered to be chronically contaminated. Comparison of the results from this survey for Σ DDTs and Σ PCBs in rock oysters from the Gulf of Oman with similar measurements made at the same locations over the past two decades indicates a temporal trend of overall decreasing Σ PCB concentrations in oysters, whereas Σ DDTs levels have little changed during that period.

Phase distribution of hydrocarbons in the water column after a pelagic deep ocean oil spill.

Spills from wrecks are a potential major source of pollution in the deep ocean. However, not much is known about the fate of a spill at several kilometers depth, beyond the oceans continental shelves. Here, we report the phase distribution of hydrocarbons released from the wrecks of the Prestige tanker, several years after it sank in November 2002 to depths between 3500 and 3800 m. The released oil reached the surface waters above the wrecks without any signs of weathering and leaving an homogenous signature throughout the water column. At depths of several kilometers below the sea surface, the occurrence and spread of the deep sea oil spill could be evaluated better by quantifying and characterizing the dissolved hydrocarbon signature, rather than just the investigation of hydrocarbons in the suspended particulate matter.

A survey of antifoulants in sediments from Ports and Marinas along the French Mediterranean coast.

Due to deleterious effects on non-target organisms, the use of organotin compounds on boat hulls of small vessels (<25 m) has been widely prohibited. The International Maritime Organisation (IMO) resolved that the complete prohibition on organotin compounds acting as biocides in antifouling systems should commence in 2008. As a result of restrictions on the use of organotin based paints, other antifouling formulations containing organic biocides have been utilised. This survey was conducted to assess the contamination of replacement biocides in the marine environment following the ban of TBT-based paints. Surface sediments samples were collected in the major ports and marinas along the France Mediterranean coastline (Cote d'Azur) and analysed for organotin compounds, Irgarol 1051, Sea-nine 211, Chlorothalonil, Dichlofluanid and Folpet. Every port and marina exhibited high levels of organotin compounds, with concentrations in sediments ranging from 37 ng Sn g(-1) dry wt in Menton Garavan to over 4000 ng Sn g(-1) dry wt close to the ship chandler within the port of Villefranche-sur-Mer. TBT degradation indexes suggested that fresh inputs are still made. Among the other antifoulants monitored, only Irgarol 1051 exhibited measurable concentrations in almost every port, with concentrations ranging from 40 ng g(-1) dry wt (Cannes) to almost 700 ng g(-1) dry wt (Villefranche-sur-Mer, ship chandler).

Utility of 5A molecular sieves to measure carbon isotope ratios in lipid biomarkers.

A procedure using 5A zeolite sorption to separate cyclic/branched organic compounds from the linear ones was developed and carbon isotopic fractionation effects were investigated in different families of compounds, e.g. within the hydrocarbon and alcohol compounds. The 5A sieve has a pore size such that only linear components can be incorporated into the pores whereas the cyclic/branched compounds are remaining free in the organic solution. The sorbed compounds were released from the molecular sieve with HF and solvent extracted with hexane. The method enables the isolation of linear saturated classes, such as n-alkanes and n-fatty alcohols from branched/cyclic compounds without isotopic fractionation for compound-specific isotope analysis (CSIA) of delta(13)C. However, alkene hydrocarbons, sterols and some aromatics were completely or partly degraded with the molecular sieve.

Chlorinated hydrocarbons in marine biota and coastal sediments from the Gulf and Gulf of Oman.

The spatial distribution of various organochlorinated compounds was investigated in the Gulf and Gulf of Oman based on marine biota (fish and various bivalves) and coastal sediment collected in Bahrain, Oman, Qatar and the United Arab Emirates (UAE) during 2000-2001. Several potential organic contaminants from agricultural (e.g., DDT and its breakdown products, lindane, endrin, dieldrin, endosulfan) and industrial (PCBs) sources were measured. Sediment burdens for all compounds, even for an apparent hot spot near a refinery in Bahrain, were amongst the lowest reported for surface sediments from other seas. Concentrations of DDTs were low in the muscle and liver of all fish (orange spotted grouper and the spangled emperor) analysed. Similarly, the levels of chlorinated hydrocarbons were low in the various bivalve species, notably rock oysters and pearl oysters. These results contribute to the sparse regional database for organochlorinated compounds in the marine environment. Moreover, they can be used as the most recent end point for elucidating temporal trends. Whereas the levels, albeit relatively low, SigmaDDTs in the rock oysters from the Gulf of Oman have remained uniform, there has been an irregular but generally decreasing trend in concentrations of summation SigmaPCBs during the last two decades.

Aliphatic and aromatic hydrocarbons in marine biota and coastal sediments from the Gulf and the Gulf of Oman.

The composition and spatial distribution of aliphatic and polycyclic aromatic hydrocarbons (PAHs) were investigated in biota and coastal sediments from four countries surrounding the Gulf (Bahrain, Qatar, United Arab Emirates and Oman). The levels of total petroleum hydrocarbons (TPH), aliphatic unresolved mixture and PAHs in sediments and biota were relatively low compared to world-wide locations reported to be chronically contaminated by oil. Only in the case of the sediments collected near the BAPCO oil refinery in Bahrain, having concentrations of 779 microg g(-1) total petroleum hydrocarbon equivalents and 6.6 microg g(-1) Sigma PAHs, can they be categorized as chronically contaminated. Some evidence of oil contamination was also apparent in sediments and bivalves around Akkah Head and Abu Dhabi in the UAE, and near Mirbat in Oman. Contaminant patterns in sediments and biota indicated that the PAHs were mainly from fossil sources, with the exception of the high PAH concentrations in sediments near the BAPCO refinery that contained substantial concentrations of carcinogenic PAH combustion products.

Isolation of neutral and acidic lipid biomarker classes for compound-specific-carbon isotope analysis by means of solvent extraction and normal-phase high-performance liquid chromatography.

An analytical method for the quantitative determination of neutral and acidic lipid biomarkers in particulate and sediment samples has been developed. The method involves a first step with solvent extraction to isolate the neutral from the acidic compounds and a second step using normal-phase HPLC on a Nucleosil silica column to separate four different classes of neutral compounds: (1) aliphatic hydrocarbons, (2) aromatic hydrocarbons, (3) ketone compounds and (4) sterol and alcohol compounds. Recoveries of the individual spiked lipid biomarkers for the whole analytical procedure ranged from 88 to 106% for fatty acids, from 50 to 60% for aliphatic hydrocarbons (> or = n-C17), from 50 to 60% for polycyclic aromatic hydrocarbons (PAHs) (> or = 3 rings), 83% for friedelin and 60-80% for the sterol and alcohol compounds. The isolated compound classes were analysed by gas chromatography-combustion-isotope ratio mass spectrometry to measure the stable carbon isotope ratios in the individual compounds. The method enables the isolation of compound classes without fractionation for compound-specific carbon isotope analysis (delta13C). This analytical protocol has been applied, and proved suitable, for the determination of lipid biomarkers (sterols, fatty alcohols and fatty acids) in marine particulate material and for the determination of PAHs in sediment samples.

Organochlorinated compounds in Caspian Sea sediments.

Several organochlorinated contaminants, including numerous pesticides, were determined in coastal sediments from the Caspian Sea. The most important contaminants were p,p'-DDT (up to 7400 pg g(-1)) and its breakdown products, p,p'-DDD (up to 3400 pg g(-1)) and p,p'-DDE (up to 1300 pg g(-1)). Although the contamination was most severe in Azerbaijan, the sediment concentrations and percentage distribution of the three DDT-related compounds indicated that such contamination constitutes a contemporary and ubiquitous problem in the Caspian Sea. Lindane represented the second most significant contaminant, particularly in the Russian Federation, with concentrations up to 609 pg g(-1). The concentrations of HCB and other chlorinated pesticides (cis- and trans-chlordane, methoxychlor, heptachlor, heptachlor epoxide, aldrin, endrin, and endosulfans) were lower and not generally of concern, but the pesticides did demonstrate markedly different distributions reflecting differing agricultural usage in the region. The concentrations of Sigma PCBs were also quite low and ranged from 0.03 to 6.4 ng g(-1), with the highest amounts in the Russian Federation and Azerbaijan.

Aliphatic and aromatic hydrocarbons in coastal Caspian Sea sediments.

This investigation represents the first extensive study of the spatial distribution and sources of aliphatic (n-alkanes and unresolved complex mixture of fossil hydrocarbons) and polycyclic aromatic hydrocarbons (PAHs) in coastal sediments from the Caspian Sea. PAH concentrations, n-alkanes and biomarker profiles all suggested that there was limited petrogenic contamination in the shallow North Caspian Sea sediments, which are coarse with a low total organic carbon content. In contrast, moderate to high petrogenic contamination was found in the South Caspian Sea, in particular in the offshore oil fields near Baku, Azerbaijan. Contaminant patterns indicated that the PAHs were mainly from fossil sources, with higher contributions of pyrolytic only near industrialized and urban areas. A high contribution of perylene, a geochemically derived PAH, to the total PAHs was found in the west and south at sites influenced by the Kura, Safid Rud, Terek, Sulak and Samur Rivers.