A first estimation of the role of penguin guano on copper cycling and organic speciation in Antarctic coastal waters.

Cu is a vital micronutrient, but free Cu ions (Cu2+) in seawater, even at subnanomolar concentrations, can impede phytoplankton growth. Natural Cu complexation with organic ligands regulates Cu acquisition and, in most instances, reduces Cu2+ concentrations below toxic thresholds. Along the Antarctic coast, the sources and sinks of Cu and its associated ligands remain poorly defined. Despite the high productivity in the area, there are no studies on the role of trophic transfer in Cu cycling. This study explores penguin guano release of Cu and Cu ligands and its potential in neutralizing copper toxicity along the Antarctic coast. We collected guano in a Chinstrap penguin nesting location in the West coast of Deception Island and extracted its components into aqueous solution imitating natural processes. Copper concentration in guano was 0.4 mg (dry weight g)-1 constituting a potential toxic threat and showed biomagnification with respect to krill. Surface seawater samples collected from various locations varying in penguin activity, were analyzed to assess the potential influence of guano on the area. Visual examination and elevated levels of Al suggested that a substantial portion of guano was lithogenic. Consequently, only a modest 16 % of the total Cu present in guano could be extracted using mechanical methods. Notably, the concentrations of the extracted organic ligands were approximately 23 times higher than the concentrations of the extracted Cu. This significant presence of ligands effectively nullifies any potential toxicity that could have arisen from free Cu2+ ions. Guano ligands' conditional stability constants were lower than those in surface seawater suggesting phytoplankton exudation was the main ligand source in the area. Overall, guano acts as a key node for Cu cycling in coastal Antarctic waters but its deleterious potential is neutralized by ligands from krill digestion and the high background concentration of phytoplankton exudates.

Penguin guano trace metals release to Antarctic waters: A kinetic modelling.

Penguin guano has been considered as a suitable bioindicator of the exposure to environmental contaminants in Antarctic environment. Although trace metal content values in penguin guano have been widely reported, the kinetics of their mobility in seawater have not been determined. In the present study, we have estimated the release rate of dissolved Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn from Gentoo (Pygoscelis papua) penguins guano to Antarctic seawater by 120 h laboratory and at external natural conditions of temperature and light experiments. A mathematical model using two metal pools guano (labile and equilibrium) and seawater compartments considering pseudo-first-order kinetics, is proposed in order to interpret and predict the release of trace metals. A good statistical agreement between experimental and modelled concentration values allows us obtention of kinetic parameters and partition coefficients (Kdi). These values allow to estimate releases into seawater from 5400 to 6.3 µg/day·penguin of Cu and V, respectively. More than 50 % of the initial content of all the studied elements are released during the first two hours, reaching 90 % release in the decreasing order of speed Ni â‰« Cu ≈ Mo > Mn > Co > Cd ≈ Pb; periods of up to one hour, Fe, V and Zn reach a maximum release and are then readsorbed. Equilibrium releases >90 % for Mo and Cd, and 55 % - 46 % for Co, Ni, Pb and Mn are obtained; Zn with 5.4 %, V with 1.7 % and Fe with 0.88 % show the lowest values. With an overwhelming growth of estimated population south of 60°S of 259.750 breeding pairs we estimate that the Gentoo penguin population is releasing annually in the Southern Ocean, 716 kg Cu, 188 kg Mn, 113 kg Fe, 102 kg Zn, 17.7 kg Mo, 12.0 kg Ni, 8.70 kg Cd, 4.59 kg Co, 6.27 kg Pb and 0.790 kg V of soluble metals.

The contribution of penguin guano to the Southern Ocean iron pool.

Iron plays a crucial role in the high-nutrient, low-chlorophyll Southern Ocean regions, promoting phytoplankton growth and enhancing atmospheric carbon sequestration. In this area, iron-rich Antarctic krill (Euphausia superba) and baleen whale species, which are among their main predators, play a large role in the recycling of iron. However, penguins have received limited attention despite their representing the largest seabird biomass in the southern polar region. Here, we use breeding site guano volumes estimated from drone images, deep learning-powered penguin census, and guano chemical composition to assess the iron export to the Antarctic waters from one of the most abundant penguin species, the Chinstrap penguin (Pygoscelis antarcticus). Our results show that these seabirds are a relevant contributor to the iron remobilization pool in the Southern Ocean. With an average guano concentration of 3 mg iron g-1, we estimate that the Chinstrap penguin population is recycling 521 tonnes iron yr-1, representing the current iron contribution half of the amount these penguins were able to recycle four decades ago, as they have declined by more than 50% since then.

Coastal gradients of small microplastics and associated pollutants influenced by estuarine sources.

Small microplastics (SMPs) in the gulf of Cadiz was sampled at 5 m depth by pumping it through the ship's pipe system and filtered through a 45 µm mesh size net. Our study reveals that higher densities have been found (130 mg·m-3) compared to other regions worldwide and these densities decreased from the coastline to the outer stations, showing a general coastal gradient influenced by estuarine outflows. SMPs with a size range between 45 and 193 µm were predominant and most of them composed by polyethylene and polypropylene. The metals associated with the MPs were mainly Na (21.1%), K (11.3%), Fe (8.5%), Ca (2.1%), Cr (1.8%), Zr (13.3%) and Hf (0.7%). The high proportion of Zr compared to Fe, which is different from what can be found in the environment, suggests that this metal is intrinsic to the materials used in catalytic processes during plastic production.

Trace elements in Antarctic penguins and the potential role of guano as source of recycled metals in the Southern Ocean.

Penguins dominate the Antarctic avifauna. As key animals in the Antarctic ecosystem, they are monitored to evaluate the ecological status of this pristine and remote region and specifically, they have been used as effective bioindicators suitable for long-term monitoring of metals in the Antarctic environment. However, studies about the role of this emblematic organism could play in the recycling of trace metals (TMs) in the Antarctic ecosystem are very limited. In this study we evaluate, using the peer review research articles already published and our own findings, the distribution of metals (i.e., Ca, Fe, Al, Na, Zn, Mg, Cu, K, Cd, Mn, Sr, Cr, Ni, Pb, Hg, V, Ba, Co, La, Ag, Rb, Hf, Sc, Au and Cs) and metalloids (As and Sb), measured in different biotic matrices, with emphasis on guano, of the Chinstrap (Pygoscelis antarcticus), Adélie (Pygoscelis adeliae) and Gentoo (Pygoscelis papua) penguins. Regarding bioactive metals, the high concentrations (µg g-1 dry weight) of Cu (2.0 ± 1.4) x 102, Fe (4.1 ± 2.9) x 102, Mn (30 ± 34) and Zn (210 ± 90) reported in the guano from all the penguin species studied including our data, are of the same order of magnitude as those reported for whale feces (µg g-1 dry weight): Cu (2.9 ± 2.4) x 102, Fe (1.5 ± 1.4) x 102, Mn (28 ± 17) and Zn (6.2 ± 4.3) x 102, and one order of magnitude higher than the metal contents in krill (µg g-1 dry weight) of Cu (10.2 ± 5.5), Fe (24 ± 29) and Zn (13.5 ± 1.7). This suggest that penguin's excretion products could be an important source of these essential elements in the surface water, with an estimated annual release on a breeding season for Cu, Fe, Mn, Zn respectively of 28, 56, 4 and 29 tons, for the Chinstrap, Adélie and Gentoo penguins. The results provide evidence on the potential influence of penguins recycling TMs in the surface layer of the water column.

A new approach for the determination of sunscreen levels in seawater by ultraviolet absorption spectrophotometry.

Sunscreen is released into the marine environment and is considered toxic for marine life. The current analytical methods for the quantification of sunscreen are mostly specific to individual chemical ingredients and based on complex analytical and instrumental techniques. A simple, selective, rapid, reproducible and low-cost spectrophotometric procedure for the quantification of commercial sunscreen in seawater is described here. The method is based on the inherent properties of these cosmetics to absorb in the wavelength of 300-400 nm. The absorption at 303 nm wavelength correlates with the concentration of most commercial sunscreens. This method allows the determination of sunscreens in the range of 2.5-1500 mg L-1, it requires no sample pretreatment and offers a precision of up to 0.2%. The spectrophotometric method was applied to quantify sunscreen concentrations at an Atlantic Beach with values ranging from 10 to 96.7 mg L-1 in the unfiltered fraction and from the undetectable value to 75.7 mg L-1 in the dissolved fraction. This method is suggested as a tool for sunscreen quantifications in environmental investigations and monitoring programs.

Repellency and mortality effects of sunscreens on the shrimp Palaemon varians: Toxicity dependent on exposure method.

Contamination by sunscreens has become a serious environmental problem due to the increasing use of these products in coastal regions. Their complex chemical composition supposes an input of different chemical compounds capable of producing toxic effects and repelling organisms. The aim of the current study was to experimentally check the repellency of three commercial sunscreens [A (lotion), B (gel) and C (milk spray)] by assessing the escape (displacement towards areas with lower sunscreen levels) of the estuarine shrimp Palaemon varians exposed (4 h) to a gradient (0-300 mg/L) of the sunscreens in a heterogeneous non-forced exposure scenario. Additionally, mortality and immobility (72 h) were checked in a traditional forced exposure scenario. Considering that the toxicity of sunscreens is a little controversial regarding their chemical availability in the medium, two different methods of sunscreen solubilisation were tested: complete homogenization and direct immersion. Very low mortality was observed in the highest concentration of sunscreens A and C applied by direct immersion; however, for sunscreen B, the main effect was the loss of motility when homogenization was applied. Repellency was evidenced for two sunscreens (A and B) applied by direct immersion. The homogenization in the medium seemed to lower the degree of repellency of the sunscreens, probably linked to the higher viscosity in the medium, preventing the motility of shrimps. By integrating both short-term responses (avoidance and mortality/immobility), the PID (population immediate decline) calculated showed that avoidance might be the main factor responsible for the reduction of the population at the local scale.

Ingestion and bioaccumulation of polystyrene nanoplastics and their effects on the microalgal feeding of Artemia franciscana.

Nanoplastics (NPs) have become one of the most serious environmental problems nowadays. The environmental issues linked to NPs are attributed to the effects after ingestion in marine organisms. Due to the incipient and controversial information about the effects of PS NPs on the feeding of organisms, the aim of this work is to assess (i) digestion dynamics of Artemia franciscana when exposed to PS NPs as the lowest concentration of PS NPs reported in toxicity test [0 (control), 0.006 and 0.6 mg·L-1] and possible interferences in the ingestion of microalgae and (ii) the accumulation and depuration of PS NPs by A. franciscana. Artemia were subjected to ingestion experiments [24 h and 3.5 h], in which the organisms were exposed to PS NPs or to PS NPs + microalgae. Post-exposure feeding (24 h exposure and 2 h feeding) and depuration (24 h exposure and 24 h of depuration) were also carried out. More than 90% of the PS NPs were ingested by Artemia and bioaccumulated in the mandible, stomach, gut, tail gut and appendages after 24 h. The ingestion of microalgae was not affected by the presence of the PS NPs. Data of post-exposure feeding indicated that Artemia previously exposed to plastic and/or microalgae presented similar microalgal ingestion (around 70%); the highest microalgal consumption (around 90%) was recorded in the treatment in which Artemia were previously starved (no plastic and no microalgae). The presence of PS NPs in the gut after the depuration experiments indicates that 24 h was not enough to eliminate the PS NPs.

Precision-Cut Tissue Slices (PCTS) from the digestive gland of the Mediterranean mussel Mytilus galloprovincialis: An ex vivo approach for molecular and cellular responses in marine invertebrates.

The precision-cut tissue slices (PCTS) represent a largely used biological model in mammalian research. This ex vivo approach offers the main advantages of in vitro systems, while maintaining the natural architecture of the tissue. The use of PCTS in toxicological research has been proposed for investigating the cellular effects of xenobiotics or bioactive compounds mostly in mammalian models. Their application is increasing also in marine organisms, but still limited to fish. This work validates the use of PCTS in an invertebrate species, the Mediterranean mussel Mytilus galloprovincialis. Intact tissue slices of different thicknesses (300, 350 and 400 µm) were successfully obtained from the digestive gland. The slices maintained the histological integrity and the viability after 6 h and 24 h incubation in culture medium, with some differences depending on the thickness. The enzymatic activities and mRNA levels of catalase and glutathione S-transferase, chosen as model biological endpoints, were measured until 24 h incubation, revealing the functionality of such systems. This work demonstrates the suitability of mussel PCTS for investigating molecular and cellular responses in ecotoxicological research.