Microplastic in marine environment: reworking and optimisation of two analytical protocols for the extraction of microplastics from sediments and oysters.

Marine sediments and sessile biota (i.e. oysters) are nowadays recognised to be affected by microplastic (MP) pollution. NOAA proposes two distinct MP extraction protocols for sandy and bed sediments, which, however, were already demonstrated to suffer from many limitations. Conversely, to what concern oysters, works already published are usually time consuming, requiring a KOH 24-48 h oxidation step. The aim of this study is to show how iterative adaptation of the NOAA protocol allows to extract MPs, included PET, from marine sediments, regardless their characteristics. The method tested on PE-LD/PET/PA/PE-HD is based on density separation and oxidation treatments which were both carefully tuned, obtaining final recoveries higher than 85% for all the micropolymers (100% for PE and PA). Furthermore, a new protocol for the extraction of MPs from oysters was assessed, highlighting its efficacy (recoveries higher than 84% for all the plastics) and time-saving peculiarity. Finally, both protocols were successfully applied in the MPs extraction from real samples from Atlantic Ocean.•The extraction of PE-LD/PET/PA/PE-HD was optimised in sediments (regardless their characteristics) and oysters.•For sediments, density separation and oxidation procedures were carefully optimised.•For oysters, oxidation times were reduced from 24 to 48 h to 1 h.

Linking contaminant distribution to hydrodynamic patterns in an urban estuary: The Douro estuary test case.

An increase in anthropogenic activities in coastal regions can put at risk their flora and fauna and their ecosystem services. Therefore, it is important to evaluate possible impacts. In particular, we need to understand the links between contaminants concentrations and the hydrodynamic patterns of these highly productive regions to anticipate the effects of contaminants in the environment. Towards that aim there is the need to carry out regular campaigns to monitor the evolution of the coastal systems. In this work we analyse in-situ measurements of physico-chemical parameters, and look for possible relations between observed contaminants patterns and estuarine hydrodynamics. Data collected in the Douro estuary, one of the main estuarine regions of the Iberian western coast, revealed the presence of 5 hazardous and noxious substances (HNS), 14 polycyclic aromatic hydrocarbons (PAHs) and 6 trace metals in water and sediment samples. Water temperature and salinity analysis revealed a strong variability, which can affect the water solubility properties and the organisms' tolerance to certain toxins. A relationship between the salinity and the HNS and PAHs concentrations was found, caused by the existence of a salt-wedge that triggers the salting-out effect. Sinker contaminants (PAHs and trace metals) can be re-suspended both during low and high flow conditions associated with the salt-wedge and with strong river flows. Floater contaminants (HNS) are completely depended on the tide, which has the capacity to distribute them through the entire estuary, during low river flow regimes. However, strong river flows, with associated river plumes, can distribute both sinker and floater contaminants to the coastal region trapping them over the inner-shelf. The results clearly show that hydrodynamic patterns are a major driver for contaminants dispersion and pathways in coastal areas, inducing harmful effects to the flora and fauna and, consequently, to the ecosystem services of these regions.

A review on the application of constructed wetlands for the removal of priority substances and contaminants of emerging concern listed in recently launched EU legislation.

The presence of organic pollutants in the aquatic environment, usually found at trace concentrations (i.e., between ng L-1 and µg L-1 or even lower, known as micropollutants), has been highlighted in recent decades as a worldwide environmental concern due to their difficult elimination by conventional water and wastewater treatment processes. The relevant information on constructed wetlands (CWs) and their application for the removal of a specific group of pollutants, 41 organic priority substances/classes of substances (PSs) and 8 certain other substances with environmental quality standards (EQS) listed in Directive 2013/39/EU as well as 17 contaminants of emerging concern (CECs) of the Watch List of Decision 2015/495/EU, is herein reviewed. Studies were found for 24 PSs and 2 other substances with EQS: octylphenol, nonylphenol, perfluorooctane sulfonic acid, di(2-ethylhexyl)phthalate, trichloromethane, dichloromethane, 1,2-dichloroethane, pentachlorobenzene, benzene, polychlorinated dibenzo-p-dioxins, naphthalene, fluoranthene, trifluralin, alachlor, isoproturon, diuron, tributyltin compounds, simazine, atrazine, chlorpyrifos (chlorpyrifos-ethyl), chlorfenvinphos, hexachlorobenzene, pentachlorophenol, endosulfan, dichlorodiphenyltrichloroethane (or DDT) and dieldrin. A few reports were also published for 8 CECs: imidacloprid, erythromycin, clarithromycin, azithromycin, diclofenac, estrone, 17-beta-estradiol and 17-alpha-ethinylestradiol. No references were found for the other 17 PSs, 6 certain other substances with EQS and 9 CECs listed in EU legislation.

Effect of petroleum hydrocarbons in copper phytoremediation by a salt marsh plant (Juncus maritimus) and the role of autochthonous bioaugmentation.

This work aimed to investigate, under controlled but environmental relevant conditions, the effects of the presence of both inorganic and organic contaminants (copper and petroleum hydrocarbons) on phytoremediation potential of the salt marsh plant Juncus maritimus. Moreover, bioaugmentation, with an autochthonous microbial consortium (AMC) resistant to Cu, was tested, aiming an increase in the remediation potential of this plant in the presence of a co-contamination. Salt marsh plants with sediment attached to their roots were collected, placed in vessels, and kept in greenhouses, under tidal simulation. Sediments were contaminated with Cu and petroleum, and the AMC was added to half of the vessels. After 5 months, plants accumulated significant amounts of Cu but only in belowground structures. The amount of Cu was even higher in the presence of petroleum. AMC addition increased Cu accumulation in belowground tissues, despite decreasing Cu bioavailability, promoting J. maritimus phytostabilization potential. Therefore, J. maritimus has potential to phytoremediate co-contaminated sediments, and autochthonous bioaugmentation can be a valuable strategy for the recovery and management of moderately impacted estuaries. This approach can contribute for a sustainable use of the environmental resources. Graphical abstract ᅟ.

Determination of 3-mercaptopropionic acid by HPLC: A sensitive method for environmental applications.

The organic sulfur compound 3-mercaptopropionic acid (3-MPA) is an important thiol intermediate in organic sulfur metabolism in natural environments. It is generated during degradation of sulfur-containing amino acids (e.g. methionine) and from demethylation of dimethylsulfoniopropionate (DMSP). This pathway is an alternative enzymatic process in the DMSP catabolism that routes sulfur away from the climatically-active dimethyl sulfide (DMS). 3-MPA detection and subsequent quantification in different matrices is difficult due to its extreme reactivity. We therefore developed a sensitive method for determination of 3-MPA based on pre-column derivatization with monobromobimane and analysis by high-performance liquid chromatography (HPLC) with fluorescence detection. This methodology was first tested with 3-MPA standards under low (0.005-0.2µmolL(-1)) and high (1-25µmolL(-1)) concentrations. For the optimization of the reaction, CHES and, alternatively, Tris-HCl buffers were evaluated in the derivatization step, with Tris-HCl showing more effective separation of thiol derivatives and a better 3-MPA peak shape. The detection limit was 4.3nmolL(-1) with a 10µL sample injection, and mean recoveries of 3-MPA ranged from 97 to 105% in estuarine waters with different salinities (0.17 and 35.9ppt). The linearity (r>0.99) and repeatability of detector response, with intra- and inter-day precision (% CV) of 2.68-7.01% and 4.86-12.5%, respectively, confirmed the reliability of the method. Previous 3-MPA analytical methods required immediate analysis due to unstable derivatives, but in this method we achieved high stability of the derivatized samples when stored at 4°C, with only a 3-5% loss after more than one year of storage. This method was successfully applied to measure 3-MPA concentrations and rates of 3-MPA production in a variety of intertidal estuarine sediment slurries. Dissolved 3-MPA concentrations in these sediment slurries varied between 2 and 237µmolL(-1) and, 3-MPA net fluxes ranged in wet sediments between -3.6±1.7 and 30±5µmolL(-1)g(-1)h(-1). Thus, the application of this optimized methodology showed an efficient performance for measuring 3-MPA in environmental samples, with a straightforward sample derivatization and a simple analysis of stable 3-MPA derivatives.

Copper phytoremediation by a salt marsh plant (Phragmites australis) enhanced by autochthonous bioaugmentation.

Here we evaluated whether the potential of Phragmites australis to phytoremediate Cu contaminated sediments could be enhanced by bioaugmentation with an autochthonous microorganism consortium (AMC) that is resistant to Cu. Saltmarsh plants with sediment attached to their roots were collected, placed in vessels and kept in greenhouses, under tidal simulation. Sediments were contaminated with Cu and the AMC was added to half of the vessels. After two months, plants accumulated significant amounts of Cu (2-10 times more) in all tissues although in higher amounts (7-10 times more) in belowground structures. AMC addition increased Cu bioavailability (5-10%) in sediments leading to a decrease in belowground structures biomass. However, bioaugmentation increased Cu translocation, with higher amounts (2 times more) of Cu in the plant stems, without significant visual toxicity signs. Therefore, autochthonous bioaugmentation can increase Cu phytoextraction potential of P. australis, which can be a valuable strategy for the recovery and management of moderately impacted estuaries.