Trajectories of trace element accumulation in seagrass (Posidonia oceanica) over a decade reveal the footprint of fish farming.

To evaluate the effect of trace element (TE) release from fish farms on seagrass Posidonia oceanica, we compared TE concentrations (As, Cd, Co, Cu, Mn, Mo, Ni, Pb, V, Zn) in shoots near fish cages (Station 'Cage') with those away from them (Station 'Control') in two fish farm facilities (Site 1 and Site 2, North Aegean Sea, Greece). We assessed the present (i.e., 2021, year of sampling) and past (reconstructed period 2012-2020) accumulation of TEs using the living compartments (leaf blades, sheaths, rhizomes, roots, epiphytes) and the dead sheaths, respectively. We also assessed possible seagrass degradation by reconstructing past rhizome production. P. oceanica rhizome production at the 'Cage' stations was up to 50% lower than at the 'Control' stations. Most TE concentrations were higher at 'Cage' stations, but the differences often depended on the seagrass living compartment. Significant differentiation between 'Cage' and 'Control' stations was observed based on the TE concentrations of the dead sheaths during 2012-2020. The contamination level at the 'Cage' stations was mostly moderate in Site 1 and low in Site 2, during the reconstructed period, while an increasing contamination trend was found for certain potential phytotoxic TEs (As, Cu, Cd, Mo, V). Our results emphasize the need for the aquaculture industry to work towards a more ecologically aware approach.

Holothurians play an important role in mitigating the impacts of aquaculture on sediment conditions.

As deposit feeders contribute to bioremediation and nutrient recycling in sediments, positively impacting water and sediment quality, holothurians are candidate organisms for multitrophic aquaculture. This study aimed to investigate the potential of Holothuria poli to reduce the environmental footprint of fish farms through a benthocosm experiment. The experimental setup included four benthocosms with holothurians(H+) and four without (H-). The 58-day experiment included two phases: constant organic enrichment and recovery. In order to simulate the organic enrichment sediment conditions under a typical fish farm, a mixture of fish feces and fish feed pellets was added. Results showed that holothurians effectively reduced organic matter and H2S and increased redox, RPD depth and sediment oxygenation, thereby preventing anoxic conditions. Also, during the recovery phase, holothurians facilitated rapid sediment recovery, while the sediments without holothurians remained organic-enriched until the end of the experiment. The study emphasizes the significance of holothurians in mitigating the impacts of aquaculture on sediment conditions and so promoting environmental sustainability.

Investigating the behavior of ultratrace levels of nanoparticulate and ionic silver in a seawater mesocosm using single particle inductively coupled plasma - mass spectrometry.

Silver nanoparticles (AgNPs) nowadays appear in close to 24% of consumer products that contain engineered nanomaterials. Thus, they are expected to be released into the environment, where their fate and effect are still undetermined. Considering the evidenced efficacy of the single particle Inductively Coupled Plasma - Mass Spectrometry (sp ICP-MS) technique in the study of nanomaterials, this work reports on the use of sp ICP-MS along with an online dilution sample introduction system for the direct analysis of untreated and spiked seawater samples, as part of a larger scale experiment studying the fate of Ag (ionic and nanoparticles) in seawater mesocosm systems. Silver nanoparticles coated with branched polyethyleneimine (BPEI@AgNPs) or ionic silver (Ag+) were introduced gradually into the seawater mesocosm tanks at very low, environmentally relevant concentrations (50 ng Ag L-1 per day, for 10 consecutive days, up to a total of 500 ng Ag L-1), and samples were collected and analyzed daily, within a consistent time window. Using very low detector dwell time (75 µs) and specialized data treatment, information was obtained on the nanoparticles' size distribution and particle number concentration, as well as the ionic silver content, of both the AgNPs and the Ag+ treated seawater mesocosm tanks. The results for the AgNP treated samples indicated the rapid degradation of the added silver particles, and the subsequent increase of ionic silver, with recoveries close to 100% for the first days of the experiment. On the other hand, particle formation was observed in the Ag+ treated seawater tanks, and even though the number concentration of silver-containing nanoparticles increased throughout the experiment, the amount of silver per particle remained relatively constant from the early days of the experiment. In addition, the online dilution sample introduction system for the ICP-MS proved capable of handling the untreated seawater matrix without significant contamination issues and downtime, while the low dwell time and data treatment procedure developed were shown to be suitable for the analysis of nanomaterials at the low nm-scale, despite the complex and heavy matrix introduced into the ICP-MS.

Passive-Sampler-Derived PCB and OCP Concentrations in the Waters of the World─First Results from the AQUA-GAPS/MONET Network.

Persistent organic pollutants (POPs) are recognized as pollutants of global concern, but so far, information on the trends of legacy POPs in the waters of the world has been missing due to logistical, analytical, and financial reasons. Passive samplers have emerged as an attractive alternative to active water sampling methods as they accumulate POPs, represent time-weighted average concentrations, and can easily be shipped and deployed. As part of the AQUA-GAPS/MONET, passive samplers were deployed at 40 globally distributed sites between 2016 and 2020, for a total of 21 freshwater and 40 marine deployments. Results from silicone passive samplers showed α-hexachlorocyclohexane (HCH) and γ-HCH displaying the greatest concentrations in the northern latitudes/Arctic Ocean, in stark contrast to the more persistent penta (PeCB)- and hexachlorobenzene (HCB), which approached equilibrium across sampling sites. Geospatial patterns of polychlorinated biphenyl (PCB) aqueous concentrations closely matched original estimates of production and use, implying limited global transport. Positive correlations between log-transformed concentrations of Σ7PCB, ΣDDTs, Σendosulfan, and Σchlordane, but not ΣHCH, and the log of population density (p < 0.05) within 5 and 10 km of the sampling sites also supported limited transport from used sites. These results help to understand the extent of global distribution, and eventually time-trends, of organic pollutants in aquatic systems, such as across freshwaters and oceans. Future deployments will aim to establish time-trends at selected sites while adding to the geographical coverage.

Decline of seagrass (Posidonia oceanica) production over two decades in the face of warming of the Eastern Mediterranean Sea.

The response of Posidonia oceanica meadows to global warming of the Eastern Mediterranean Sea, where the increase in sea surface temperature (SST) is particularly severe, is poorly investigated. Here, we reconstructed the long-term P. oceanica production in 60 meadows along the Greek Seas over two decades (1997-2018), using lepidochronology. We determined the effect of warming on production by reconstructing the annual and maximum (i.e. August) SST, considering the role of other production drivers related to water quality (i.e. Chla, suspended particulate matter, Secchi depth). Grand mean (±SE) production across all sites and the study period was 48 ± 1.1 mg DW per shoot yr-1 . Production over the last two decades followed a trajectory of decrease, which was related to the concurrent increase in annual SST and SSTaug . Annual SST > 20°C and SSTaug > 26.5°C was related to production decline (GAMM, P < 0.05), while the rest of the tested factors did not help explain the production pattern. Our results indicate a persistent and increasing threat for Eastern Mediterranean meadows, drawing attention to management authorities, highlighting the necessity of reducing local impacts to enhance the resilience of seagrass meadows to global change threats.

Marine plastics alter the organic matter composition of the air-sea boundary layer, with influences on CO2 exchange: a large-scale analysis method to explore future ocean scenarios.

Microplastics are substrates for microbial activity and can influence biomass production. This has potentially important implications in the sea-surface microlayer, the marine boundary layer that controls gas exchange with the atmosphere and where biologically produced organic compounds can accumulate. In the present study, we used six large scale mesocosms to simulate future ocean scenarios of high plastic concentration. Each mesocosm was filled with 3 m3 of seawater from the oligotrophic Sea of Crete, in the Eastern Mediterranean Sea. A known amount of standard polystyrene microbeads of 30 µm diameter was added to three replicate mesocosms, while maintaining the remaining three as plastic-free controls. Over the course of a 12-day experiment, we explored microbial organic matter dynamics in the sea-surface microlayer in the presence and absence of microplastic contamination of the underlying water. Our study shows that microplastics increased both biomass production and enrichment of carbohydrate-like and proteinaceous marine gel compounds in the sea-surface microlayer. Importantly, this resulted in a ∼3 % reduction in the concentration of dissolved CO2 in the underlying water. This reduction was associated to both direct and indirect impacts of microplastic pollution on the uptake of CO2 within the marine carbon cycle, by modifying the biogenic composition of the sea's boundary layer with the atmosphere.

Intensive marine finfish aquaculture impacts community structure and metal bioaccumulation in meso-zooplankton.

Commercial aquaculture has a profound impact on coastal marine environments. Here, we investigate the spatial impact of intensive commercial finfish aquaculture on local meso-zooplankton communities and the bioaccumulation of aquaculturally-derived metals (and other elements) within zooplankton samples in the Vourlias Bay, Greece. The results indicate alterations to zooplankton community composition correlate with increased eutrophic compound concentrations in the water column in closer proximity to aquaculture stations (100-300 m from fish cages). During the summer sampling, higher concentrations of accumulated metals within zooplankton samples were found at reference stations furthest from fish cages (>1000 m). During the winter sampling, however, spatial differences in accumulated metal concentrations were limited. We suggest metals are rapidly accumulated at lower trophic levels near aquaculture stations and are then dispersed to greater distances while ascending the trophic chain. This research provides good evidence for future investigations into zooplankton as an environmental impact bioindicator for aquaculture.

Fish farming, metals and antibiotics in the eastern Mediterranean Sea: Is there a threat to sediment wildlife?

Chemical residues released from aquaculture farms may persist in the environment and may pose adverse ecological effects. The aim of this study was to assess the pollution status of marine sediments underneath or close to aquaculture farms in the Eastern Mediterranean Sea, the factors that affect the elemental distribution, and the exceedance of environmental quality standards and factors. To this end, surface sediment samples were collected (underneath fish cages, at 25 m distance and from a reference station) from 48 fish farms in Greece with variable environmental and geochemical characteristics. The content of 29 metals and major and trace elements, and three antibiotics (oxytetracycline, florfenicol, and flumequine), was determined in the sediment samples. Most of the elements found in the sediments originated from geological sources and their concentrations were close to Earth's Crust content. Below and close to fish farm cages, the sediment was enriched with P, Cu, Zn, Mo, and Cd mainly due to the aquaculture biosolid deposition, and changes in environmental conditions (increased organic matter, low redox potential). Cr and As were found to exceed twice the upper threshold limit of the available sediment quality guidelines in 13.5% and 7.3% of sampling stations, respectively. The potential ecological risk of V, Cr, Mn, Co, Ni, Cu, Zn, As and Pb was found to be low in the sediment close to fish cages except for Cd, which may pose a moderate to considerable risk in 12.5% of sampled fish farms. However, the estimated risks for this metal may be influenced by the high background levels found in the investigated areas. This study also shows that the occurrence of antibiotics in sediments below fish farms in the Eastern Mediterranean Sea is very sparse (i.e., only flumequine was found in two farms) and concentration levels are relatively low.

Viral Metagenomic Content Reflects Seawater Ecological Quality in the Coastal Zone.

Viruses interfere with their host's metabolism through the expression of auxiliary metabolic genes (AMGs) that, until now, are mostly studied under large physicochemical gradients. Here, we focus on coastal marine ecosystems and we sequence the viral metagenome (virome) of samples with discrete levels of human-driven disturbances. We aim to describe the relevance of viromics with respect to ecological quality status, defined by the classic seawater trophic index (TRIX). Neither viral (family level) nor bacterial (family level, based on 16S rRNA sequencing) community structure correlated with TRIX. AMGs involved in the Calvin and tricarboxylic acid cycles were found at stations with poor ecological quality, supporting viral lysis by modifying the host's energy supply. AMGs involved in "non-traditional" energy-production pathways (3HP, sulfur oxidation) were found irrespective of ecological quality, highlighting the importance of recognizing the prevalent metabolic paths and their intermediate byproducts. Various AMGs explained the variability between stations with poor vs. good ecological quality. Our study confirms the pivotal role of the virome content in ecosystem functioning, acting as a "pool" of available functions that may be transferred to the hosts. Further, it suggests that AMGs could be used as an ultra-sensitive metric of energy-production pathways with relevance in the vulnerable coastal zone and its ecological quality.

Metals in sardine and anchovy from Greek coastal areas: Public health risk and nutritional benefits assessment.

Concentrations of 26 metals and elements were measured in sardine (Sardina pilchardus) and anchovy (Engraulis encrasicolus) sampled from 6 Greek coastal areas in order to assess public health risks and benefits. Nutritional benefits seem to outweigh the potential risks arising from fish metal content, since various parameters (Safety Standards, Estimated Daily Intake, Maximum Safe Consumption, Hazard Quotient, Metal Pollution Index, As Carcinogenic Risk, Mercury toxicity - Selenium benefits, Nutrient Reference Values) indicated mostly safe consumption of the studied species. Weekly consumption of 480.76 g of sardine and anchovy poses minor risks (due to increased levels of essential metals like Fe and Zn in some cases) but great benefits regarding intake of essential elements like Mg, Fe, Cu, Zn, Mo, Ca, P, Se. The traces of inorganic As detected were well below all safety limits. Hg toxicity symptoms are not likely to appear and Se benefits are not likely to be compromised.

Can intensive fish farming for 20 years induce changes in benthic ecosystems on a scale of waterbody? An assessment from Cephalonia bay (Ionian Sea).

The environmental impacts of fish farming on benthic ecosystems beneath the fish cages have been widely addressed the past decades. However, the chronic release of nutrients can cause a shift in local primary productivity and a chronic increase in the sedimentation of organic material at a large spatial scale which could be reflected in benthic ecosystems. In this context, the indirect effects of aquaculture on the benthic ecosystem were studied in a semi-closed bay (Cephalonia, Ionian Sea) where a relatively large fish farm has been operating since 1982. Results from the present sampling were compared to historical data obtained in 1996 and 2001, in order to detect if nutrient release that could impact phytoplankton dynamics in the bay could indirectly alter benthic communities, as well. Macrofaunal communities have not shown deterioration but rather a small, yet statistically significant, improvement in diversity indices and ecological status indicators, and no significant change regarding bioturbation potential. This indicated that processes involved in nutrient consumption and transfer are highly effective in such an oligotrophic environment.

Metals and elements in sardine and anchovy: Species specific differences and correlations with proximate composition and size.

Species - specific differences in the levels of 26 metals and elements in sardine and anchovy are investigated and the factors of proximate composition (proteins, lipids, ash) and body size (length, weight) that may affect the metal and elemental concentrations in fish are explored. Statistical analysis revealed that levels of metals and elements in fish seem to strongly depend on species. Significantly higher levels of most of the metals and elements studied have been observed in anchovy compared to sardine at each of six different sites. The observed species-specific differences in metal content could be attributed to different proximate composition and size among other factors. The significant (positive or negative) correlations found between lipids, proteins, ash, weight, length and metals or elements, suggest that higher levels of most of the metals and elements studied can be associated with lower lipid content, greater protein and ash content and smaller size.

Arsenic speciation in fish from Greek coastal areas.

Arsenic speciation analysis was conducted on fish samples (sardine and anchovy) collected from six areas along the Greek coastline, i.e. Artemisium Straits, Thermaikos Gulf, Amvrakikos Gulf, Strymonian Gulf, Thracian Sea, and Elefsina Gulf. Total arsenic levels ranging from 11.8 to 62.6mg As/kg dry weight were determined. Arsenobetaine, a non-toxic form of arsenic, was found to be the main arsenic species, present at 8.6 to 58.8mg As/kg dry weight, accounting for 67-95% of the total arsenic. Also detected in all fish samples was dimethylarsinic acid, although at considerably lower concentrations, ranging from 0.072-0.956mg As/kg dry weight. Monomethylarsonic acid was detected at low levels in all anchovy samples, and only in sardines from one area. Finally, inorganic arsenic in the form of arsenate was detected only in fish at one area, indicating the possible effect of an environmental parameter on its presence at detectable amounts. Statistical analysis revealed the environmental variables, such as salinity, total organic carbon and nitrogen, ammonium, phosphate, total phosphorus, dissolved oxygen and pressure index, are potentially correlated to As species concentrations. Furthermore, based on factor analysis, the biological parameters, such as fish weight, lipids, protein and ash content, that are correlated to As species concentrations of fish were also identified. The interrelationship of arsenobetaine and dimethylarsinic acid concentrations within each fish species was evaluated.

The impact of silver nanoparticles on marine plankton dynamics: Dependence on coating, size and concentration.

During this study, three microcosm experiments were carried out with natural coastal seawater, collected in the Eastern Mediterranean Sea, in order to assess the effect of silver nanoparticle (AgNP) exposure to natural plankton communities. The impact of coating (branched-polyethyleneimine: BPEI vs. poly-vinylpyrrolidone: PVP), size (40 vs. 60nm), concentration (200, 500, 2000, 5000 and 10,000ng Ag L-1) and silver form (dissolved Ag+ vs. AgNPs) were tested. The results of chlorophyll a concentration revealed that PVP AgNPs caused a higher toxicity than BPEI AgNPs, and this was possibly related to the measured higher dissolution rate. Additionally, toxicity of BPEI AgNPs was size-dependent, with 40 being more toxic than 60 nm AgNPs, which was nevertheless not seen clearly for PVP AgNPs. Interestingly, community composition altered in response to AgNP exposure: cyanobacterial abundance was negatively affected at concentrations ≥200ng Ag L-1, and dinoflagellate abundance and composition were altered at a 2000ng Ag L-1 concentration. Specifically, dinoflagellate (Gymnodinium, Prorocentrum and Gyrodinium) and diatom (Nitzschia, Navicula and Climacosphenia) genera either increased or decreased, highlighting taxa-specific effects, with some of them being able to tolerate, compensate or even benefit from AgNPs. Silver in either form (dissolved Ag+ or in NPs) caused almost identical results in the plankton community, further indicating that Ag+ release is the primary cause of AgNP toxicity. This study employed for the first time environmentally relevant AgNP concentrations (minimum 200ng Ag L-1) in natural seawater without pre-filtration steps and showed that community changes were driven by the exposure but were largely dependent on ambient physico-chemical characteristics and should be further investigated.

Silver nanoparticles in seawater: A dynamic mass balance at part per trillion silver concentrations.

This study investigates the dynamic processes affecting silver (Ag) nanoparticles that have been spiked into seawater at environmentally relevant concentrations (200 and 2000ngAgL-1). Seawater samples were taken at regular time intervals from multiple microcosm tanks and analysed rapidly, without any sample preparation, using a recently developed flow injection on-line dilution single particle inductively coupled plasma mass spectrometry method. Dissolution was found to be the predominant process of Ag nanoparticle transformation, with its rate being influenced by the type and thickness of the nanoparticle organic coating. More specifically the branched poly(ethyleneimine) coating provided additional stability to the 40 and 60nmAg nanoparticles that were tested, compared to the poly(vinylpyrrolidone) coated ones. At high Ag nanoparticle spiking levels and after 24h of exposure an extra Ag-containing nanoparticle peak appeared at the low range of the NP size distribution histogram. This peak corresponds to Ag-containing particles that contain Ag mass equivalent to 25-30nm Ag nanoparticles (assuming spherical shape). However, the composition and the "real" size of these particles remains unknown as the particles may have formed from the in-situ reduction of dissolved silver or they originate from other processes involving nanocrystal formation, as has been shown to occur in sewage sludge, or interaction with natural organic matter. Overall, this study provides additional insight into the physicochemical mechanisms behind Ag nanoparticle behavior in marine media.

Aquatic Global Passive Sampling (AQUA-GAPS) Revisited: First Steps toward a Network of Networks for Monitoring Organic Contaminants in the Aquatic Environment.

Organic contaminants, in particular persistent organic pollutants (POPs), adversely affect water quality and aquatic food webs across the globe. As of now, there is no globally consistent information available on concentrations of dissolved POPs in water bodies. The advance of passive sampling techniques has made it possible to establish a global monitoring program for these compounds in the waters of the world, which we call the Aquatic Global Passive Sampling (AQUA-GAPS) network. A recent expert meeting discussed the background, motivations, and strategic approaches of AQUA-GAPS, and its implementation as a network of networks for monitoring organic contaminants (e.g., POPs and others contaminants of concern). Initially, AQUA-GAPS will demonstrate its operating principle via two proof-of-concept studies focused on the detection of legacy and emerging POPs in freshwater and coastal marine sites using both polyethylene and silicone passive samplers. AQUA-GAPS is set up as a decentralized network, which is open to other participants from around the world to participate in deployments and to initiate new studies. In particular, participants are sought to initiate deployments and studies investigating the presence of legacy and emerging POPs in Africa, Central, and South America.

Mussel farming in Maliakos Gulf and quality indicators of the marine environment: Good benthic below poor pelagic ecological status.

Biological and geochemical variables in the water column and sediments were monitored along a transect of a mussel farm located in a transitional environment in Maliakos Gulf, a semi-enclosed gulf in eastern Mediterranean. Analyses of water, sediment and macrofauna samples were used to calculate ecological status indicators in the context of the European Water Framework Directive. The water column ecological status was "Poor" or "Bad" showing little change with distance from the farm, but the ecological status of the benthic communities was found to be "Good," although there were quantitative changes in macrofaunal indices with distance from the farm.

PAHs and n-alkanes in Mediterranean coastal marine sediments: aquaculture as a significant point source.

The occurrence of polycyclic aromatic and aliphatic hydrocarbons in fish feed, sediment trap material and marine sediments was examined at two fish farms in the eastern Mediterranean. The average (min-max) concentrations of polycyclic aromatic hydrocarbons (PAHs) in fish feed and particulate effluents were 316 (287-351) ng g(-1) DW and 487 (475-499) ng g(-1) DW, respectively. Lower PAH levels were determined in the underlying marine sediments. In the surface sediments under the farms (0 m distance from the edge of the cages) and in the immediate vicinity, the concentration levels of n-alkanes and PAHs were significantly higher than in the surrounding sediments in both sites. PAHs and n-alkanes individual component profiles of fish feed and sinking material were similar with the corresponding profiles of the sediment samples collected in the immediate vicinity around the cages. On a daily basis, the average PAH sedimentation fluxes under the cages was 24.4 microg m(-2) d(-1), which is considerably higher compared with the observed PAH sedimentary fluxes in the open eastern Mediterranean. Our results imply that fish farming is a significant source of these persistent organic pollutants (POPs) in the marine environment and therefore a likely change in the scale of production might introduce new sources of environmental risk. Further work is required in order to develop an appropriate monitoring system for the sustainable development of the aquaculture sector.

Effects of fish farm waste on Posidonia oceanica meadows: synthesis and provision of monitoring and management tools.

This paper provides a synthesis of the EU project MedVeg addressing the fate of nutrients released from fish farming in the Mediterranean with particular focus on the endemic seagrass Posidonia oceanica habitat. The objectives were to identify the main drivers of seagrass decline linked to fish farming and to provide sensitive indicators of environmental change, which can be used for monitoring purposes. The sedimentation of waste particles in the farm vicinities emerges as the main driver of benthic deterioration, such as accumulation of organic matter, sediment anoxia as well as seagrass decline. The effects of fish farming on P. oceanica meadows are diverse and complex and detected through various metrics and indicators. A safety distance of 400 m is suggested for management of P. oceanica near fish farms followed by establishment of permanent seagrass plots revisited annually for monitoring the health of the meadows.

Diurnal cycle of PAHs, nitro-PAHs, and oxy-PAHs in a high oxidation capacity marine background atmosphere.

To improve our understanding of the formation and fate of nitro-PAHs, which contribute to the toxicity of ambient particles, the diurnal variation of their ambient concentration was studied concurrently with the corresponding PAH, OH radical, ozone, and oxy-PAH concentration, during an intensive field campaign at an eastern Mediterranean marine background location (Finokalia, Island of Crete) in August, 2001. The gas-phase PAH and OH radical concentrations maximized at noon. Gas-phase PAH concentrations were correlated (p < 0.001) with ambient temperatures. The gas-phase OH-radical-initiated PAH reaction was identified as the major process contributing to the ambient burden of nitro-PAHs. 2-Nitrofluoranthene and 2-nitropyrene were the most abundant particle-associated nitro-PAHs. A well-defined diurnal pattern was identified for both compounds exhibiting a maximum during midday followed by a rapid decrease. 9,10-Anthracenodione and 9-fluorenone, the most abundant oxy-PAHs, did not present a diurnal variation of concentration.