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The present work extends the scope of prior studies through analysis, modelling and simulation of the As, Cd, Co, Cu, Fe Mn, Mo, Ni and Zn release from Gentoo (Pygoscelis papua) and Chinstrap (Pygoscelis antarcticus) penguin guano to the Southern Ocean seawater and to Antarctic snow meltwater. Laboratory experimental results have been modelled considering kinetic processes between water and guano using two element pools in the guano compartment; its application allows us to interpret behaviours and predict release concentrations of dissolved trace elements from guano which are potentially useful for incorporation as elements source into biogeochemical models applied in the Southern Ocean. Variations in quantities and release patterns depending on the type of guano and aqueous medium in contact have been identified. The release percentages from the guano to the aqueous medium, once the steady state has been reached, vary depending on the water medium and guano type in the ranges of 100-2.9 % for Mo; 91.5-68.6 % for Ni; 81.8-22.8 % As; 52.0-43.9 % Cu; 26.9-7.4 % Mn; 24.9-5.4 for Co; 4.4-3.2 % for Zn and 0.94-0.51 % for Fe. Considering a penguin population of 774,000 Gentoo and 8,000,000 Chinstrap, the estimated annual mass released to the both seawater and freshwater would be ≈18,500 kg for Cu, ≈1710 kg for Zn, ≈1944 kg for Fe, ≈1640 kg for Mn, ≈499 kg for As, ≈289 kg for Ni, ≈155 kg for Mo, ≈36.7 kg for Cd and ≈8.1 kg for Co. These contributions can be locally significant both in promoting phytoplankton growth and in their role as inhibitors of primary productivity., Competing Interests: Declaration of competing interest The authors declare that they have no know competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

The 2021 Tajogaite eruption in La Palma (Canary Islands, Spain) emitted vast volumes of lava during 85 days, which reached the ocean in several occasions at the western flank of the island. Most of these flows merged to create a primary lava delta, covering an area of 48 ha, with an additional 30 ha underwater. Here we characterize the effects of the lava-seawater interaction on the surrounding marine environment. The area was sampled during two multidisciplinary oceanographic cruises: the first one comprised the days before the lava reached the ocean and after the first contact; and the second took place a month later, when the lava delta was already formed but still receiving lava inputs. Physical-chemical anomalies were found in the whole water column at different depths up to 300 m in all measured parameters, such as turbidity (+9 NTU), dissolved oxygen concentration (-17.17 μmol kg -1 ), pH T25 (-0.1), and chlorophyll-a concentration (-0.33 mg m -3 ). Surface temperature increased up to +2.3 °C (28.5 °C) and surface salinity showed increases and decreases of -1.01 and +0.70, respectively, in a radius of 4 km around the lava delta. In the water column, the heated waters experimented a lava-induced upwelling, bringing deeper, nutrient-rich waters to shallower depths; however, this feature did not trigger any phytoplankton bloom. In fact, integrated chlorophyll-a showed an abrupt decrease of -41 % in just two days and -69 % a month later, compared to prior conditions. The chlorophyll-a depletion reached a distance larger than 2.5 km (not delimited)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

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., Competing Interests: No authors have competing interests.

The environmental conditions of semi-enclosed coastal water-bodies are directly related to the catchment, human activities, and oceanographic setting in which they are located. As a result of low tidal forcing, and generally weak currents, waters in Mediterranean harbours are poorly renewed, leading to quality deterioration. Here, we characterise the seasonal variation of trace metals (i.e. Co, Cd, Cu, Fe, Mo, Ni, Pb, and Zn) in surface waters, and trace metal content in sediments from Maó Harbour, a semi-enclosed coastal ecosystem in the NW Mediterranean Sea. Our results show that most of the dissolved trace metals in the waters of Maó Harbour exhibit a marked inner-outer concentration gradient, suggesting a permanent input into the inner part of the harbour. In general, metal concentrations in the waters of Maó Harbour are higher than those in offshore waters. Concentration of Cu (21±8nM), Fe (9.2±3.2nM) and Pb (1.3±0.4nM) are particularly high when compared with other coastal areas of the Mediterranean Sea. The concentration of some metals such as Cu and Zn increases during summertime, when the human population and boat traffic increase during the tourism season, and when resuspension from the metal enriched sediments is higher. The evaluation of the metal sources in the harbour reveals that, compared with other putative sources such as runoff, aerosol deposition and fresh groundwater discharges, contaminated sediments are the main source of the metals found in the water column, most likely through vessel-driven resuspension events. This study contributes to the understanding of the processes that control the occurrence and distribution of trace metals in Maó Harbour, thus aiding in the effective management of the harbour, and enhancing the overall quality of the seawater ecosystem., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Thiols are compounds of paramount importance in the cellular metabolism due to their double detoxifying role as radical scavengers and trace metal ligands. However, we have scarce information about their extracellular cycling as limited data are available about their concentration, stability and speciation in the aquatic medium. In natural waters, they form part of the pool of reduced sulfur substance (RSS) whose presence has been documented by voltammetric and chromatographic methods. Traditional use of cathodic stripping voltammetry (CSV) for the analysis of RSS could only give an overall concentration due to the coalescence of their CSV peaks. Recently, it has been shown that the use of multiple deposition potentials could take voltammetry of RSS to a higher level, permitting the identification and quantification of the mixtures of RSS despite showing as a single coalescent peak. Here, due to its similarity with classical pseudopolarography, we propose to rename this analytical strategy as cathodic pseudopolarography (CP) and we present for the first time its use for the analysis of mixes of low molecular weight thiols (LMWT) at the nanomolar level. Despite limitations caused by the identical behavior of some LMWT, the CP allowed to isolate the contribution of cysteine and cystine from a coalescent signal in LMWT mixtures. Sample handling with clean protocols allowed the direct determination of the cystine:cysteine ratio without sample modification. Finally, we show the application of CP to identify LMWT in seawater samples extracted from benthic chambers and suggest future applications in other areas of environmental electroanalysis., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A growing awareness of the risks associated with skin exposure to ultraviolet (UV) radiation over the past decades has led to increased use of sunscreen cosmetic products leading the introduction of new chemical compounds in the marine environment. Although coastal tourism and recreation are the largest and most rapidly growing activities in the world, the evaluation of sunscreen as source of chemicals to the coastal marine system has not been addressed. Concentrations of chemical UV filters included in the formulation of sunscreens, such as benzophehone 3 (BZ-3), 4-methylbenzylidene camphor (4-MBC), TiO₂ and ZnO, are detected in nearshore waters with variable concentrations along the day and mainly concentrated in the surface microlayer (i.e. 53.6-577.5 ng L⁻¹ BZ-3; 51.4-113.4 ng L⁻¹ 4-MBC; 6.9-37.6 µg L⁻¹ Ti; 1.0-3.3 µg L⁻¹ Zn). The presence of these compounds in seawater suggests relevant effects on phytoplankton. Indeed, we provide evidences of the negative effect of sunblocks on the growth of the commonly found marine diatom Chaetoceros gracilis (mean EC₅₀ = 125±71 mg L⁻¹). Dissolution of sunscreens in seawater also releases inorganic nutrients (N, P and Si forms) that can fuel algal growth. In particular, PO₄³⁻ is released by these products in notable amounts (up to 17 µmol PO₄³⁻g⁻¹). We conservatively estimate an increase of up to 100% background PO₄³⁻ concentrations (0.12 µmol L⁻¹ over a background level of 0.06 µmol L⁻¹) in nearshore waters during low water renewal conditions in a populated beach in Majorca island. Our results show that sunscreen products are a significant source of organic and inorganic chemicals that reach the sea with potential ecological consequences on the coastal marine ecosystem.

Thiols and thioamides form part of the pool of reduced sulfur substances (RSS) that modify the health of aquatic ecosystems acting as radical scavengers and heavy metal ligands. Their concentrations could be easily determined in seawater by cathodic stripping voltammetry (CSV) were it not be for the coalescence of their responses in a single peak. Here, we modified the traditional CSV method of RSS analysis to allow individual recognition and quantification in thiol/thioamide mixes. Glutathione, cysteine, thiourea and thioacetamide in UV digested seawater were repeatedly analyzed shifting the deposition potential (E(dep)) in the range +0.07 to -0.4V at high resolution. The representation of peak height (i(p)) and peak potential (E(p)) vs E(dep) resulted in different and distinctive profiles for each substance that allowed the selection of adequate E(dep) ranges for their separate quantification. Copper saturation modified thiol profiles and cancelled the response of thioamides. The vs E(dep) profiles explained the nature of the different thiols and thioamides present in the sample and permitted their individual quantification with excellent accuracy. The utility of the method was put to test with seawater modified with natural unknown RSS from pore waters and Posidonia oceanica exudates. Although both samples gave similar CSV signals, the vs E(dep) profiles unveiled completely different electrochemical behaviors incompatible with a similar nature. Based on those profiles we hypothesized that pore waters released a glutathione/thiourea mix and that one or several unidentified RSS formed part of P. oceanica exudates. The analytical scheme proposed here opens a new door to the use of direct voltammetry in the qualitative and quantitative determination of RSS in natural waters., (Copyright © 2012 Elsevier B.V. All rights reserved.)

A high-performance liquid chromatography method was developed for the separation and determination of four cobalamins in seawater. Chromatographic separation was performed on a reversed-phase discovery RP-amide C(16) column with buffer potassium dihydrogenphosphate and acetonitrile as the mobile phases in linear gradients elution mode. Cobalamins were previously preconcentrated in C(18) resins cartridges. Detection was performed using UV-diode array detector in a range of λ of 200-400 nm. The method showed to be linear over a range of 1-300 ng mL(-1) with acceptable precision and accuracy. The detection limits ranged between 0.07 pg mL(-1) for 5'-deoxyadenosylcobalamin and 0.5 pg mL(-1) for hydroxocobalamin. The mean cobalamins recoveries for direct determination ranged between 76 and 93% for hydroxo-, cyano- and methylcobalamin, while the recovery for 5'-deoxyadenosylcobalamin was only 31% suggesting that the preconcentration method was not valid for this cobalamin. The method was successfully applied to coastal seawater where the concentrations ranged from 4.2 to 7.3 ng L(-1) for hydroxo-, 1.4-3.9 ng L(-1) for cyano-, 2.1-4.6 ng L(-1) for 5'-deoxyadenosyl- and 33-83.5 ng L(-1) for methylcobalamin., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Deception Island (DI) is an active volcanic caldera in the South Shetland Islands, Antarctica, with an inner bay, Port Foster, formed by an ancient eruption. The bay's seafloor hydrofracture system contains hydrothermal seeps and submarine vents, which are a source of trace metals (TMs) like Fe, Ni, Co, V, and greenhouse gases (GHGs) such as CO2 and CH4. This study presents measurements of TMs and GHGs in Port Foster's surface waters during January-February 2021 to characterize their spatial distribution. TMs concentrations in the northeastern region of the bay, particularly V (74 nM), Fe (361 nM), Co (3.9 nM) and Ni (17.2 nM), were generally higher than in the Southern Ocean, likely due to hydrothermal activity. As some TMs such as Fe are scarce in the SO and limit primary productivity, inputs of these nutrients from DI into surrounding waters may also regionally promote increased primary productivity. Higher surface temperature (ST), elevated partial pressure of CO2 (pCO2), and lower salinity were found near submarine fumaroles, with ST positively correlated with pCO2 and negatively with salinity. Although hydrothermal sites showed localized CO2 outgassing, the bay overall acted as a CO2 sink, with a median flux of -2.78 mol m-2 yr-1 with an interquartile range (IQR) of 3.84 mol m-2 yr-1. CH4 highest concentration levels were found in the southeastern sector. The median concentration was 8.9 nM with an IQR of 1.9 nM, making Port Foster a regional net CH4 source with a median flux of 9.7 μmol m-2 d-1 and an IQR of 3.4 μmol m-2 d-1. Ultimately, the analysis of spatial patterns of the measured variables suggested that fumaroles of DI may be playing a significant role in the alteration of regional seawater biogeochemistry. [ABSTRACT FROM AUTHOR]

This study reports the only recent characterization of two contrasted wet deposition events collected during the PEACETIME (ProcEss studies at the Air–sEa Interface after dust deposition in the MEditerranean Sea) cruise in the open Mediterranean Sea (Med Sea) and their impact on trace metal (TM) marine stocks. Rain samples were analysed for Al, 12 TMs (Co, Cd, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Ti, V and Zn) and nutrient (N, P, dissolved organic carbon) concentrations. The first rain sample collected in the Ionian Sea (Rain ION) was a typical regional background wet deposition event, whereas the second rain sample collected in the Algerian Basin (Rain FAST) was a Saharan dust wet deposition event. Even in the remote Med Sea, all background TM inputs presented an anthropogenic signature, except for Fe, Mn and Ti. The concentrations of TMs in the two rain samples were significantly lower compared to concentrations in rains collected at coastal sites reported in the literature, due to the decrease in anthropogenic emissions during the preceding decades. The atmospheric TM inputs were mainly dissolved forms, even in dusty Rain FAST. The TM stocks in the mixed layer (ML, 0–20 m) at the FAST station before and after the event showed that the atmospheric inputs were a significant supply of particulate TMs and dissolved Fe and Co for surface seawater. Even if the wet deposition delivers TMs mainly in soluble form, the post-deposition aerosol dissolution could to be a key additional pathway in the supply of dissolved TMs. At the scale of the western and central Mediterranean, the atmospheric inputs were of the same order of magnitude as ML stocks for dissolved Fe, Co and Zn, highlighting the role of the atmosphere in their biogeochemical cycles in the stratified Med Sea. In case of intense dust-rich wet deposition events, the role of atmospheric inputs as an external source was extended to dissolved Co, Fe, Mn, Pb and Zn. Our results suggest that the wet deposition constitutes only a source of some of dissolved TMs for Med Sea surface waters. The contribution of dry deposition to the atmospheric TM inputs needs to be investigated. [ABSTRACT FROM AUTHOR]

Ice-nucleating particles (INPs) have a large impact on the climate-relevant properties of clouds over the oceans. Studies have shown that sea spray aerosols (SSAs), produced upon bursting of bubbles at the ocean surface, can be an important source of marine INPs, particularly during periods of enhanced biological productivity. Recent mesocosm experiments using natural seawater spiked with nutrients have revealed that marine INPs are derived from two separate classes of organic matter in SSAs. Despite this finding, existing parameterizations for marine INP abundance are based solely on single variables such as SSA organic carbon (OC) or SSA surface area, which may mask specific trends in the separate classes of INP. The goal of this paper is to improve the understanding of the connection between ocean biology and marine INP abundance by reporting results from a field study and proposing a new parameterization of marine INPs that accounts for the two associated classes of organic matter. The PEACETIME cruise took place from 10 May to 10 June 2017 in the Mediterranean Sea. Throughout the cruise, INP concentrations in the surface microlayer (INPSML) and in SSAs (INPSSA) produced using a plunging aquarium apparatus were continuously monitored while surface seawater (SSW) and SML biological properties were measured in parallel. The organic content of artificially generated SSAs was also evaluated. INPSML concentrations were found to be lower than those reported in the literature, presumably due to the oligotrophic nature of the Mediterranean Sea. A dust wet deposition event that occurred during the cruise increased the INP concentrations measured in the SML by an order of magnitude, in line with increases in iron in the SML and bacterial abundances. Increases in INPSSA were not observed until after a delay of 3 days compared to increases in the SML and are likely a result of a strong influence of bulk SSW INPs for the temperatures investigated (T=-18 ∘C for SSAs, T=-15 ∘C for SSW). Results confirmed that INPSSA are divided into two classes depending on their associated organic matter. Here we find that warm (T≥-22 ∘C) INPSSA concentrations are correlated with water-soluble organic matter (WSOC) in the SSAs, but also with SSW parameters (particulate organic carbon, POCSSW and INPSSW,-16C) while cold INPSSA (T<-22 ∘C) are correlated with SSA water-insoluble organic carbon (WIOC) and SML dissolved organic carbon (DOC) concentrations. A relationship was also found between cold INPSSA and SSW nano- and microphytoplankton cell abundances, indicating that these species might be a source of water-insoluble organic matter with surfactant properties and specific IN activities. Guided by these results, we formulated and tested multiple parameterizations for the abundance of INPs in marine SSAs, including a single-component model based on POCSSW and a two-component model based on SSA WIOC and OC. We also altered a previous model based on OCSSA content to account for oligotrophy of the Mediterranean Sea. We then compared this formulation with the previous models. This new parameterization should improve attempts to incorporate marine INP emissions into numerical models. [ABSTRACT FROM AUTHOR]

Highlights: [•] MSFIA-LWCC system to analyze Ti in seawater, sediment and seagrasses samples. [•] A versatile and simple method for Ti determination in environmental samples. [•] New digestion method using K2S2O8 to disaggregate TiO2 nanoparticles. [Copyright &y& Elsevier]

Abstract: Major advances in analytical chemistry and instrumentation have prompted major advances in our understanding of trace metal biogeochemistry. However, the deep-water concentration of most trace elements has not been yet assessed across broad regions of the oceans. A synthesis of data on trace metals (i.e. Cd, Co, Cu, Mo, Ni, Pb and Zn) measured and reported for depths 1000m or deeper, between 1976 and 2009 revealed major gaps in our coverage of this key property. Cadmium and Cu have been the elements more extensively measured with 264 and 210 deep profiles reported in 64 and 57 articles, respectively, while Mo and Co have been reported only at 17 and 60 ocean sites, respectively. Globally 68.1% (216.1 106 km2) of deep oceans (1000m or deeper) have not been sampled. The bulk of depth profiles published in peer reviewed scientific literature are from the Northern hemisphere (69.7% of the total reported profiles) rendering the Southern hemisphere as a poorly explored region for these important properties (mainly in the South and Eastern Pacific Ocean and in the Tropical Indian Ocean). Vertical profiles of dissolved elements plotted with data compiled during the last 34years indicate that, in addition to the variation of concentrations, vertical distributions differs per ocean basin. [Copyright &y& Elsevier]