Compounds In Marine Sediments Research Articles

Determination of organotin compounds in marine sediments from Arctic Svalbard and West Antarctic Fildes Peninsula

This study investigated the contamination levels of five typical organotin compounds in Arctic and Antarctic marine sediments. Organotin total concentrations ranged from not detected (ND) to 37.9 ng Sn/g dw and from ND to 34.0 ng Sn/g dw in surface sediments of Svalbard and Fildes Peninsula, respectively. Dibutyltin accounted for 11.3 %–100 % of butyltins in Arctic sediments, whilst diphenyltin was the predominant phenyltin species in both Arctic and Antarctic. However, the concentrations of tributyltin and triphenyltin were lower than low-substituted organotins in the study areas, indicating the effectiveness of international ban on the use of triorganotin-based antifouling paints. No significant difference in organotin contamination was found between Arctic and Antarctic, although the time suffered from human interference was shorter in the Antarctic. Overall, these data can provide a diagnosis of recent organotin inputs in polar regions and serve as a baseline for future study assessing their local applications.

High wax ester and triacylglycerol biosynthesis potential in coastal sediments of Antarctic and Subantarctic environments.

The wax ester (WE) and triacylglycerol (TAG) biosynthetic potential of marine microorganisms is poorly understood at the microbial community level. The goal of this work was to uncover the prevalence and diversity of bacteria with the potential to synthesize these neutral lipids in coastal sediments of two high latitude environments, and to characterize the gene clusters related to this process. Homolog sequences of the key enzyme, the wax ester synthase/acyl-CoA:diacylglycerol acyltransferase (WS/DGAT) were retrieved from 13 metagenomes, including subtidal and intertidal sediments of a Subantarctic environment (Ushuaia Bay, Argentina), and subtidal sediments of an Antarctic environment (Potter Cove, Antarctica). The abundance of WS/DGAT homolog sequences in the sediment metagenomes was 1.23 ± 0.42 times the abundance of 12 single-copy genes encoding ribosomal proteins, higher than in seawater (0.13 ± 0.31 times in 338 metagenomes). Homolog sequences were highly diverse, and were assigned to the Pseudomonadota, Actinomycetota, Bacteroidota and Acidobacteriota phyla. The genomic context of WS/DGAT homologs included sequences related to WE and TAG biosynthesis pathways, as well as to other related pathways such as fatty-acid metabolism, suggesting carbon recycling might drive the flux to neutral lipid synthesis. These results indicate the presence of abundant and taxonomically diverse bacterial populations with the potential to synthesize lipid storage compounds in marine sediments, relating this metabolic process to bacterial survival.

A Guideline Value for Dioxin-Like Compounds in Marine Sediments.

Sediments to be dredged as part of the installation of a harbor crossing in Sydney, Australia, contained measurable concentrations of dioxin-like compounds. To assess the suitability of these sediments for ocean disposal, a defensible sediment quality guideline value (SQGV) for dioxin-like compounds, expressed as pg toxic equivalent (TEQ)fish /g dry weight, was required. There were deemed to be too many uncertainties associated with a value derived using effects data from field studies. A similar issue was associated with values based on equilibrium partitioning from sediment to pore water, largely associated with the wide range of reported sediment:water partition coefficients. Greater certainty was associated with the use of a tissue residue approach based on equilibrium partitioning between sediment and organisms determined using tissue concentrations in fish, the most sensitive aquatic biota, and biota:sediment accumulation factors. The calculation of an appropriate SQGV used data for dioxin-like compounds in both fish and sediments from Sydney Harbor. A conservative SQGV for dioxin-like compounds of 70 pg TEQ/g dry weight was deemed to be adequately protective of biota that might be exposed to these contaminants in sediments at the ocean spoil ground. The approach is transferable to similar situations internationally. Environ Toxicol Chem 2023;42:257-271. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Occurrence, sources, and risk assessment of unconventional polycyclic aromatic compounds in marine sediments from sandy beach intertidal zones

This study investigated the concentrations of polycyclic aromatic compounds (PACs), including parent polyaromatic hydrocarbons (PAHs) and their nitrated and oxygenated derivatives, in 48 sediment samples from the intertidal region of sandy beaches in Baía de Todos os Santos (BTS), Salvador, State of Bahia, Brazil. The total PAH (∑PAH) concentration, total nitro-PAH (∑nitro-PAH) concentration, and total oxy-PAH (∑oxy-PAH) concentration ranged from 2.11 μg g−1 dry weight (dw) to 28.0 μg g−1 dw, 2.58 μg g−1 dw to 30.2 μg g−1 dw, and 0.34 μg g−1 dw to 3.65 μg g−1 dw, respectively. Elevated concentrations of parent PAHs and nitro-PAHs were found in samples from two sites in BTS, which were also characterized by high percentages of fine–medium sand and low organic matter contents. Potent mutagenic 3-nitrobenzanthrone (3-NBA) was found in 86% of the samples at concentrations ranging from 0.200 μg g−1 dw to 0.690 μg g−1 dw. Furthermore, calculations of the benzo[a]pyrene toxicity equivalency (BaPTEQ) indicated that three carcinogenic high-molecular-weight PAHs accounted for 98.7% of the total maximum PAH concentration. Finally, we assessed the possible environmental risks posed to benthic species living in the sediments of BTS. The results showed that the risk quotient for PAHs (RQPAHs) was ≥1. In turn, the summed RQ for all PACs (∑RQmixture) ranged from 1 to 30, but did not exceed the maximum allowable threshold; thus, the risks posed to benthic species were moderate for all sediment samples.

A potential suite of climate markers of long-chain n-alkanes and alkenones preserved in the top sediments from the Pacific sector of the Southern Ocean

Investigating organic compounds in marine sediments can potentially unlock a wealth of new information in these climate archives. Here, we present pilot study results of organic geochemical features of long-chain n-alkanes and alkenones and individual carbon isotope ratios of long-chain n-alkanes from a newly collected, approximately 8 m long, located in the far reaches of the Pacific sector of the Southern Ocean. We analyzed a suite of organic compounds in the core. The results show abundant long-chain n-alkanes (C29–C35) with predominant odd-over-even carbon preference, suggesting an origin of terrestrial higher plant waxes via long-range transport of dust, possibly from Australia and New Zealand. The δ13C values of the C31n-alkane range from −29.4 to −24.8‰, in which the higher δ13C values suggest more contributions from C4 plant waxes. In the analysis, we found that the mid-chain n-alkanes (C23–C25) have a small odd-over-even carbon preference, indicating that they were derived from marine non-diatom pelagic phytoplankton and microalgae and terrestrial sources. Furthermore, the C26 and C28 with lower δ13C values (~−34‰) indicate an origin from marine chemoautotrophic bacteria. We found that the abundances of tetra-unsaturated alkenones (C37:4) in this Southern Ocean sediment core ranges from 11 to 37%, perhaps a marker of low sea surface temperature (SST). The results of this study strongly indicate that the δ13C values of long-chain n-alkanes and {U}_{37}^{mathrm{k}} index are potentially useful to reconstruct the detailed history of C3/C4 plants and SST change in the higher latitudes of the Southern Ocean.

Chemical assessment of marine sediments in vicinity of Norwegian fish farms – A pilot study

While aquaculture is growing rapidly all over the world and generating many economic benefits, so have the environmental concerns about the externalities posed by the fish-farming industry. The distribution profiles of organic compounds and inorganic elements were explored in marine surface sediments collected in proximity of two active Norwegian fish farms, Hestøya and Nørholmen (<200–1100 m from the perimeter edge of the installations). Overall, the sediment organic matter (SOM) content was 7.3 ± 4.9%, with 7.9 ± 5.1% and 4.0 ± 0.5% for Hestøya and Nørholmen, respectively. A non-targeted analysis was performed for screening organic compounds in marine sediments, and the presence of 60 compounds was detected. Among suspect compounds were alkanes, alkenes, aromatics, aldehydes, ketones, esters, alcohols, diols, polycyclic aromatic hydrocarbons (PAHs), terpenes and terpenoids. Heptanal, benzaldehyde, 4-oxoisophorone, 1,7-dimethylnaphthalene and 3-bromophenol were the most abundant compounds in marine sediments. In total, concentrations of 47 elements were measured, concentrations of As, Cd, Cr, Cu, Hg, Mo, Ni, Sn and Zn were strongly influenced by anthropogenic inputs, while concentrations of Ce, Co, Al, Fe and Ti were related to the geology of the local bedrock. The chemical composition of marine sediments was different at Hestøya and Nørholmen, indicating different anthropogenic inputs in these areas. In general, concentrations of toxic elements were below the proposed guidelines for Norwegian marine sediment quality and can be characterised as background pollution. Overall, fish-farming activities had only a minor or negligible influence on marine sediments and are unlikely to cause any harm to local aquatic life in the studied area.

Herbivory and its effect on Phanerozoic oxygen concentrations

Abstract The appearance of terrestrial land plants is thought to have accompanied an increase in atmospheric oxygen levels, producing the highest O2 concentrations estimated from the geological record, and marking the transition to a permanently oxygenated deep ocean. This Paleozoic oxygenation event, which likely peaked in the Carboniferous Period, was at least partially mediated by the development of recalcitrant, carbon-rich organic compounds in terrestrial plants. A number of studies have argued that shifts in coal formation and paleogeography led to declining preservation of these compounds on land, depressing oxygen levels in the terminal Paleozoic and early Mesozoic. In contrast, we propose that the evolution and diversification of terrestrial herbivores may have limited transport and long-term burial of terrestrial organic compounds in marine sediments, resulting in less organic carbon burial and attendant declines in atmospheric oxygen. This mechanism suggests that interactions among a triad of biological processes—marine photosynthesis, land plant colonization, and the advent of herbivory—may have dictated the long-term redox state of Earth’s surface environments over the Phanerozoic Eon.

Toxic anthropogenic signature in Antarctic continental shelf and deep sea sediments

Industrial activity generates harmful substances which can travel via aerial or water currents thousands of kilometers away from the place they were used impacting the local biota where they deposit. The presence of harmful anthropogenic substances in the Antarctic is particularly surprising and striking due to its remoteness and the apparent geophysical isolation developed with the flows of the Antarctic Circumpolar current and the ring of westerly winds surrounding the continent. However, long-range atmospheric transport (LRAT) of pollutants has been detected in the Antarctic since the 70’s along the Antarctic trophic food web from phytoplankton to birds. Still, no information exists on the presence of cytotoxic compounds in marine sediments neither at basin scales (thousands of kilometers) nor in water depths (hundreds of meters) beyond shallow coastal areas near research stations. Our results showed for the first time that there is cytotoxic activity in marine sediment extracts from water depths >1000 m and along thousands of kilometers of Antarctic continental shelf, in some cases comparable to that observed in Mediterranean areas. Ongoing anthropogenic pressure appears as a serious threat to the sessile benthic communities, which have evolved in near isolation for millions of years in these environments.

The life sulfuric: microbial ecology of sulfur cycling in marine sediments.

SummaryAlmost the entire seafloor is covered with sediments that can be more than 10 000 m thick and represent a vast microbial ecosystem that is a major component of Earth's element and energy cycles. Notably, a significant proportion of microbial life in marine sediments can exploit energy conserved during transformations of sulfur compounds among different redox states. Sulfur cycling, which is primarily driven by sulfate reduction, is tightly interwoven with other important element cycles (carbon, nitrogen, iron, manganese) and therefore has profound implications for both cellular‐ and ecosystem‐level processes. Sulfur‐transforming microorganisms have evolved diverse genetic, metabolic, and in some cases, peculiar phenotypic features to fill an array of ecological niches in marine sediments. Here, we review recent and selected findings on the microbial guilds that are involved in the transformation of different sulfur compounds in marine sediments and emphasise how these are interlinked and have a major influence on ecology and biogeochemistry in the seafloor. Extraordinary discoveries have increased our knowledge on microbial sulfur cycling, mainly in sulfate‐rich surface sediments, yet many questions remain regarding how sulfur redox processes may sustain the deep‐subsurface biosphere and the impact of organic sulfur compounds on the marine sulfur cycle.

Fate and behaviour of marine organic matter during burial of anoxic sediments: Testing CH2O as generalized input parameter in reaction transport models

The precise modelling of organic matter degradation is key in unravelling the marine carbon cycle and to constrain methane and carbonate formation within sediments. So far, different model approaches for calculating organic matter degradation have been developed. The term “organic matter” is considered in different ways in the diverse models and the simplification “CH2O” is often used. In this work, we test the common approach of “CH2O” as a simplification for total degradable organic matter. The focus of our study is on shallow to 500m deep anoxic marine sediments. We performed hydrogeochemical modelling in different ocean drilling program (ODP) case studies with single organic compounds and with a mixture of organic compounds that considers the most reactive compounds in marine sediments. The modelling results indicate that the distribution of carbon species (carbonates, methane, CO2, and alkalinity) generated by the degradation of organic carbon is dependent on the type of organic matter that is given in the model for remineralization. The closer the nominal oxidation state of the organic carbon that is remineralized in the model calculations is to the oxidation state of carbon in methane (−4), the more methane is produced and less carbonates (carbon oxidation state of +4) precipitate. Simulation results suggested that the commonly and often used “CH2O” as initial input in reaction transport models is a valid simplification of complex organic matter. However, the better the model input parameters are constrained, the better will be the conclusions on the marine carbon cycle and methane formation.

Extraction of climatic signals from fossil organic compounds in marine sediments up to 11.7 Ma old (IODP-U1318)

This study focuses on the extraction of climate signals and processes using a combined approach which includes the analysis of a high number of lipid molecules in marine sediments, and the chemometric analysis of the acquired data. Neutral and acidic fractions of marine sediments from site IODP-U1318 (south-west of the UK, Porcupine Seabight) were quantified by GC–MS. The alkenone unsaturation index, Uk′37, was estimated from the composition of C37 alkenones and it was then used for the estimation of sea surface temperatures (SST) for reference. Principal component analysis (PCA), explained 77.45% of the total data variance, and differentiated neutral fraction GC–MS total ion current (TIC) profiles according to SST values of the different sediment sections. GC–MS TIC chromatograms were correlated to sea surface temperatures (SST) by partial least squares regression (PLSR). The compounds more robustly in line with SST values at each sediment section explained 93% of the SST variance and they were identified using the variable importance in projection (VIP) scores method. The proposed approach enables an objective identification of organic compounds sensitive to SST variability throughout complete chromatographic profiles. As a result of this multivariate unbiased approach, lipid composition of sediments was differentiated between compounds of marine (long chain n-alkanes, long chain n-alkan-1-ols) and terrestrial (short chain n-alkan1-ols, alkenols, cholesterol, squalene) origin, whose concentrations were directly and inversely correlated to SST, respectively.

Analysis of endocrine disruptor compounds in marine sediments by in cell clean up-pressurized liquid extraction-liquid chromatography tandem mass spectrometry determination

A less time-, solvent- and sorbent-consuming analytical methodology for the determination of bisphenol A and alkylphenols (4-tert-octylphenol, 4-octylphenol, 4-n-nonylphenol, nonylphenol) in marine sediment was developed and validated. The method was based on selective pressurized liquid extraction (SPLE) with a simultaneous in cell clean up combined with liquid chromatography-electrospray ionization tandem mass spectrometry in negative mode (LC-ESI-MS/MS). The SPLE extraction conditions were optimized by a Plackett–Burman design followed by a central composite design. Quantitation was performed by standard addition curves in order to correct matrix effects. The analytical features of the method were satisfactory: relative recoveries varied between 94 and 100% and repeatability and intermediate precision were <6% for all compounds. Uncertainty assessment of measurement was estimated on the basis of an in-house validation according to EURACHEM/CITAC guide. Quantitation limits of the method (MQL) ranged between 0.17 (4-n-nonylphenol) and 4.01ngg−1 dry weight (nonylphenol). Sensitivity, selectivity, automaticity and fastness are the main advantages of this green methodology. As an application, marine sediment samples from Galicia coast (NW of Spain) were analysed. Nonylphenol and 4-tert-octylphenol were measured in all samples at concentrations between 20.1 and 1409ngg−1 dry weight, respectively. Sediment toxicity was estimated and no risk to aquatic biota was found.

A temporal and spatial assessment of TBT concentrations at dredged material disposal sites around the coast of England and Wales

Despite legislative interventions since the 1980s, contemporary concentrations of organotin compounds in marine sediments still impose restrictions on the disposal of dredged material in the UK. Here, we analyse temporal and spatial data to assess the effectiveness of the ban on the use of TBT paints in reducing concentrations at disposal sites.At a national scale, there was a statistically significant increase in the proportion of samples in which the concentration was below the limit of detection (LOD) from 1998 to 2010. This was observed for sediments both inside and outside the disposal sites. However, this temporal decline in organotin concentration is disposal site-specific. Of the four sites studied in detail, two displayed significant increases in proportion of samples below LOD over time. We argue that site-specificity in the effectiveness of the TBT ban results from variations in historical practices at source and unique environmental characteristics of each site.

Microwave‐assisted extraction combined with on‐line solid phase extraction followed by ultra‐high‐performance liquid chromatography with tandem mass spectrometric determination of benzotriazole UV stabilizers in marine sediments and sewage sludges

Benzotriazole ultra-violet stabilisers are compounds widely used in personal care products, which can reach the environment after passing through wastewater treatment plants. In this work, we develop a novel method to evaluate the presence of seven compounds in marine sediments and sewage sludges using microwave-assisted extraction followed by a clean-up step based in on-line solid phase extraction coupled to ultra-high-performance liquid chromatography with MS/MS detection. This method allows for fast and efficient extraction from the solid matrix, subsequent automatic on-line purification and preconcentration, and analysis. For the optimised method, LOD were from 53.3 to 146 ng/kg and LOQ were in the range of 176-486 ng/kg. The method was validated for different environmental solid samples with satisfactory recoveries and relative standard deviations, between 46.1 and 83.9 and 7.8 and 15.5% (sludges) and 50.1 and 87.1% and 8.83 and 16.3% (sediments), respectively. Finally, the studied analytes were quantified in concentrations between 0.18 and 24.0 ng/g in real samples of marine sediments and sewage sludges from Gran Canaria Island (Spain).

Simultaneous Determination of Organotin Compounds in Marine Sediments by High Performance Liquid Chromatography Inductively Coupled Plasma Mass Spectrometry

Simultaneous Determination of Organotin Compounds in Marine Sediments by High Performance Liquid Chromatography Inductively Coupled Plasma Mass Spectrometry

Analytical methods and problems related to the determination of organotin compounds in marine sediments

The determination of organotin compounds in bottom sediments is a complex process that requires a number of analytical steps, i.e. sample collection, transport and storage; extraction of analytes from sediment; derivatization; extract purification; enrichment; and the final chromatographic measurement. The whole process is time and labour consuming, and subject to securing sample representativeness. In this review the most frequently encountered problems and the examples of possible analytical solutions are presented, which encompass the specific steps of speciation analysis of these toxic compounds.

Critical evaluation of various extraction procedures for the speciation of butyltin compounds in sediments

The efficiency of different extraction procedures for the simultaneous determination of butyltin compounds in marine sediments by gas chromatography–mass spectrometry (GC--MS) was critically evaluated in the present work. Three different polar solvents (acetic acid, a mixture of acetic acid with methanol, and a mixture of acetic acid, methanol, and water) and three different extraction approaches (mechanical shaking, ultrasonic, and microwave-assisted extraction) were used for the extraction of butyltin compounds from PACS-2 certified marine sediment reference material. Before determination by GC--MS, extracted butyltin species were derivatized with sodium tetraethyl borate and extracted into iso-octane. The results indicated that 30-min ultrasonic extraction with 100% acetic acid provided satisfactory recoveries for all certified butyltins. The developed analytical method was successfully applied for determination of butyltin compounds in coastal sediments of the Northern Adriatic Sea. The results demonstrated that butyltins were present in all sediments analysed.

Validated analytical strategy for the determination of polycyclic aromatic compounds in marine sediments by liquid chromatography coupled with diode-array detection and mass spectrometry

The aim of this work was to optimise and validate the experimental conditions for the analysis of 20 polycyclic aromatic compounds (PACs) [19 polycyclic aromatic hydrocarbons (PAHs) and dibenzothiophene as polycyclic aromatic sulphur heterocycle (PASH)] in marine sediments by reversed-phase high-performance liquid chromatography (LC) coupled to photodiode array detection (DAD) and to mass spectrometry (MS). The LC–MS interface used was atmospheric pressure chemical ionization (APCI) in the positive ion mode. The operational parameters of the APCI interface and MS detection, such as organic modifier, fragmentation voltage, gain, vaporizer temperature, corona current, capillary voltage, drying gas (N 2) and nebulizer pressure, were studied. The sediments were subjected to microwave-assisted solvent extraction (MAE) and clean-up by solid-phase extraction (SPE). The relevance of the selected PACs lies in the fact that 16 PACs are classified by the US Environmental Protection Agency as priority pollutants; 17 PACs are detected in the Prestige oil spill; and 8 PACs are included in the priority substance list of the EU water policy. Recoveries from 47% to 102% were obtained for SRM 1944 certified reference sediment. The limits of quantitation were lower than 100 ng g −1 dry weight for most PACs, and good precision was achieved.

Sources and fate of amino sugars in coastal Peruvian sediments

Amino sugars are involved in the marine carbon and nitrogen cycles and comprise a geochemically significant fraction of marine organic material (OM). However, information on abundance and distribution of these compounds in marine sediments is scarce. Three sediment cores (<50 cm) from the coastal region off Peru were investigated for concentrations of glucosamine (GlcN), galactosamine (GalN), mannosamine (ManN), and muramic acid (Mur). The sum of the four amino sugars accounted for 1.0–2.4% of organic carbon and 1.9–3.8% of nitrogen in the sediments. At the shallowest (102 m) and the deepest site (1278 m), carbon-normalized concentrations decreased down-core, suggesting preferential degradation of amino sugars compared to bulk sedimentary OM. At the site from the center of the oxygen minimum zone (238 m), amino sugar concentrations were high throughout the core, pointing to enhanced preservation of amino sugars under anoxic conditions. GlcN (44–56 mol%) and GalN (33–42 mol%) were the dominant amino sugars in all investigated samples, while ManN (6–14 mol%) and Mur (1–4 mol%) were significantly less abundant. Mur was predominantly associated with cell wall remains rather than with living bacteria, since bacterial abundances estimated based on Mur concentrations were up to 500 times higher than cell counts reported for sediments from this area. GlcN/GalN-ratios (1.1–1.7) indicated that chitin, a polymer of GlcN, was not a major contributor to the amino sugar pool of the investigated sediments. Furthermore, GlcN/Mur-ratios (13–68) are inconsistent with a predominant contribution of intact peptidoglycan, which exhibits a 1:1-ratio. The present study includes a compilation of previously published information on distribution and abundance of amino sugars in the marine environment. Both concentrations and ratios observed in the Peruvian sediments fall in the range of values reported for OM in water column and sediments from different oceanic regions and water depths. Although specific sources for the majority of sedimentary amino sugars remain unidentified, there are indications for a major prokaryotic origin. As suggested in previous studies, the uniform amino sugar compositions of altered marine OM and particularly the close association of GlcN and GalN, which is similar to the ratio observed in living bacteria, are consistent with a transformation of planktonic into bacterial OM.

Risks posed by trace organic contaminants in coastal sediments in the Pearl River Delta, China

Local marine environments in China’s Pearl River Delta (PRD), the most rapidly developing region in one of the world’s fastest growing economies, have been experiencing significant environmental stress during the past decades. This investigation was conducted to determine the status and trends of persistence organic pollutants (POPs) such as polycyclic aromatic hydrocarbons (PAHs), petroleum hydrocarbons (PHCs), polychlorinated biphenyls (PCBs), organochlorine (OC) pesticides and dioxin-related compounds in marine sediments collected from sixteen coastal stations in the Pearl River Delta (PRD) in March 2003. Elevated concentrations of PAHs (94–4300 ng/g), PCBs (6.0–290 ng/g), PHCs (14–150 μg/g), and DDTs (1.4–600 ng/g) were detected in sediment samples. In addition, 2,3,7,8-tetrachlorodibenzo- p-dioxin (TCDD)-like activities in the sediment samples were estimated to range from 0.3 to 440 pg TCDD-EQ/g. Sediments collected from Xiashan contained the greatest concentrations of trace organic contaminations amongst all the sampling stations in the present study. The degree of trace organic contamination was, in general, more severe at stations situated along the west shores of the PRD than their counterparts in the east. A preliminary assessment was performed to examine the probable risks to the marine ecosystem due to POPs. The results showed that OC pesticide contamination in the PRD was particularly serious and might pose a threat to the health of the marine inhabitants.