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1.
Ecol Evol ; 14(2): e11048, 2024 Feb.
Article in English | MEDLINE | ID: mdl-38380063

ABSTRACT

Eutrophication, increased temperatures and stratification can lead to massive, filamentous, N2-fixing cyanobacterial (FNC) blooms in coastal ecosystems with largely unresolved consequences for the mass and energy supply in food webs. Mesozooplankton adapt to not top-down controlled FNC blooms by switching diets from phytoplankton to microzooplankton, resulting in a directly quantifiable increase in its trophic position (TP) from 2.0 to as high as 3.0. If this process in mesozooplankton, we call trophic lengthening, was transferred to higher trophic levels of a food web, a loss of energy could result in massive declines of fish biomass. We used compound-specific nitrogen stable isotope data of amino acids (CSIA) to estimate and compare the nitrogen (N) sources and TPs of cod and flounder from FNC bloom influence areas (central Baltic Sea) and areas without it (western Baltic Sea). We tested if FNC-triggered trophic lengthening in mesozooplankton is carried over to fish. The TP of cod from the western Baltic (4.1 ± 0.5), feeding mainly on decapods, was equal to reference values. Only cod from the central Baltic, mainly feeding on zooplanktivorous pelagics, had a significantly higher TP (4.6 ± 0.4), indicating a strong carry-over effect trophic lengthening from mesozooplankton. In contrast, the TP of molluscivorous flounder, associated with the benthic food web, was unaffected by trophic lengthening and quite similar reference values of 3.2 ± 0.2 in both areas. This suggests that FNC blooms lead to a large loss of energy in zooplanktivorous but not in molluscivorous mesopredators. If FNC blooms continue to trigger the detour of energy at the base of the pelagic food web due to a massive heterotrophic microbial system, the TP of cod will not return to lower TP values and the fish stock not recover. Monitoring the TP of key species can identify fundamental changes in ecosystems and provide information for resource management.

2.
Environ Pollut ; 316(Pt 1): 120526, 2023 Jan 01.
Article in English | MEDLINE | ID: mdl-36341831

ABSTRACT

The emissions of marine diesel engines have gained both global and regional attentions because of their impact on human health and climate change. To reduce ship emissions, the International Maritime Organization capped the fuel sulfur content of marine fuels. Consequently, either low-sulfur fuels or additional exhaust gas cleaning devices for the reduction in sulfur dioxide (SO2) emissions became mandatory. Although a wet scrubber reduces the amount of SO2 significantly, there is still a need to consider the reduction in particle emissions directly. We present data on the particle removal efficiency of a scrubber regarding particle number and mass concentration with different marine fuel types, marine gas oil, and two heavy fuel oils (HFOs). An open-loop sulfur scrubber was installed in the exhaust line of a marine diesel test engine. Fine particulate matter was comprehensively characterized in terms of its physical and chemical properties. The wet scrubber led up to a 40% reduction in particle number, whereas a reduction in particle mass emissions was not generally determined. We observed a shift in the size distribution by the scrubber to larger particle diameters when the engine was operated on conventional HFOs. The reduction in particle number concentrations and shift in particle size were caused by the coagulation of soot particles and formation/growing of sulfur-containing particles. Combining the scrubber with a wet electrostatic precipitator as an additional abatement system showed a reduction in particle number and mass emission factors by >98%. Therefore, the application of a wet scrubber for the after-treatment of marine fuel oil combustion will reduce SO2 emissions, but it does not substantially affect the number and mass concentration of respirable particulate matters. To reduce particle emission, the scrubber should be combined with additional abatement systems.


Subject(s)
Air Pollutants , Fuel Oils , Aerosols , Air Pollutants/analysis , Gasoline/analysis , Particulate Matter/analysis , Sulfur/analysis , Vehicle Emissions/analysis
4.
Ambio ; 51(6): 1588-1608, 2022 Jun.
Article in English | MEDLINE | ID: mdl-34637089

ABSTRACT

The Baltic Sea is among the most polluted seas worldwide. Anthropogenic contaminants are mainly introduced via riverine discharge and atmospheric deposition. Regional and international measures have successfully been employed to reduce concentrations of several legacy contaminants. However, current Baltic Sea monitoring programs do not address compounds of emerging concern. Hence, potentially harmful pharmaceuticals, UV filters, polar pesticides, estrogenic compounds, per- and polyfluoroalkyl substances, or naturally produced algal toxins are not taken into account during the assessment of the state of the Baltic Sea. Herein, we conducted literature searches based on systematic approaches and compiled reported data on these substances in Baltic Sea surface water and on methodological advances for sample processing and chemical as well as effect-based analysis of these analytically challenging marine pollutants. Finally, we provide recommendations for improvement of future contaminant and risk assessment in the Baltic Sea, which revolve around a combination of both chemical and effect-based analyses.


Subject(s)
Pesticides , Water Pollutants, Chemical , Baltic States , Environmental Monitoring , Oceans and Seas , Seawater/chemistry , Water Pollutants, Chemical/analysis
5.
Sci Total Environ ; 798: 149171, 2021 Dec 01.
Article in English | MEDLINE | ID: mdl-34329935

ABSTRACT

The global occurrence of organic UV filters in the marine environment is of increasing ecotoxicological concern. Here we assessed the toxicity of UV filters ensulizole and octocrylene in the blue mussels Mytilus edulis exposed to 10 or 100 µg l-1 of octocrylene and ensulizole for two weeks. An integrated battery of biochemical and molecular biomarkers related to xenobiotics metabolism and cellular toxicity (including oxidative stress, DNA damage, apoptosis, autophagy and inflammation) was used to assess the toxicity of these UV filters in the mussels. Octocrylene (but not ensulizole) accumulated in the mussel tissues during the waterborne exposures. Both studied UV filters induced sublethal toxic effects in M. edulis at the investigated concentrations. These effects involved induction of oxidative stress, genotoxicity (indicated by upregulation of DNA damage sensing and repair markers), upregulation of apoptosis and inflammation, and dysregulation of the xenobiotic biotransformation system. Octocrylene induced cellular stress in a concentration-dependent manner, whereas ensulizole appeared to be more toxic at the lower (10 µg l-1) studied concentration than at 100 µg l-1. The different concentration-dependence of sublethal effects and distinct toxicological profiles of ensulizole and octocrylene show that the environmental toxicity is not directly related to lipophilicity and bioaccumulation potential of these UV filters and demonstrate the importance of using bioassays for toxicity assessment of emerging pollutants in coastal marine ecosystems.


Subject(s)
Mytilus edulis , Mytilus , Water Pollutants, Chemical , Acrylates , Animals , Benzimidazoles , Biomarkers , Ecosystem , Sulfonic Acids , Sunscreening Agents/toxicity , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/toxicity
6.
Environ Sci Pollut Res Int ; 28(29): 39296-39309, 2021 Aug.
Article in English | MEDLINE | ID: mdl-33755886

ABSTRACT

From 2001 to 2014, 13 surveys were conducted in the Baltic Sea, to determine its pollution of 50 micropollutants. The investigations focused mostly on the German western Baltic Sea; in 2008, one survey covered the entire Baltic Sea. Various groups of herbicides (such as triazines, phenoxyacetic acid, phenylurea), perfluoroalkyl substances, pharmaceuticals, and industrial products were analyzed during these surveys. The highest concentrations (median 1 to 4 ng/L) were observed for atrazine, simazine, chloridazone, 2,4-dichlorophenoxyacetic acid, benzotriazole, primidone, and carbamazepine. Most micropollutants exhibited a relatively homogenous spatial distribution, though some herbicides show elevated concentrations in certain regions (e.g., Odra estuary), indicating a riverine input. The data set was analyzed, both for seasonal influences and long-time trends. Some herbicides exhibited higher concentrations during summertime. Both upward- and downward-directed time trends could be identified for some herbicides and perfluorinated compounds. For most of the detected compounds, a low-risk quotient was calculated. Only the occurrence of carbendazim could potentially pose a higher risk to the Baltic Sea.


Subject(s)
Water Pollutants, Chemical , Baltic States , Environmental Monitoring , Estuaries , Risk Assessment , Seasons , Water Pollutants, Chemical/analysis
7.
Rapid Commun Mass Spectrom ; 35(2): e8863, 2021 Jan 30.
Article in English | MEDLINE | ID: mdl-32557743

ABSTRACT

RATIONALE: Fast and sensitive detection of aromatic hydrocarbons (AHs) in water is of high importance because of their significant impact on human health and the environment. For this, resonance-enhanced multiphoton ionization (REMPI) coupled to trap-and-release membrane-introduction mass spectrometry (T&R-MIMS) offers the possibility of sensitive on-line water analysis with a time resolution of minutes. METHODS: REMPI is a versatile tool for sensitive gas-phase analysis, in which AHs are selectively ionized in complex gas mixtures by the subsequent absorption of at least two photons. In T&R-MIMS, selective extraction and enrichment of analytes from water can be achieved using semipermeable membranes. By the subsequent stimulated desorption of enriched compounds, mass spectrometric detection is enabled. RESULTS: We present an external T&R inlet for hollow-fiber membranes coupled to REMPI time-of-flight mass spectrometry, which enables direct and sensitive detection of semi-volatile AHs in water. In laboratory experiments, spiked water samples were analyzed. For the investigated compounds, limits of detection (LODs) in the range 1-47 ng/L were determined. The LODs are approximately one order of magnitude lower than in a previously reported continuous membrane-introduction approach using a planar membrane. Further improvement of LOD may be realized by extending the trapping time and by increasing the release temperature. Furthermore, the system was applied to investigate different fuels suspended in water and real water samples. The obtained data are in good agreement with findings of a former study. CONCLUSIONS: In the framework of the present study, we demonstrate the high potential of the combination of REMPI and T&R-MIMS in the form of a newly developed external hollow-fiber membrane inlet. With the developed system, semi-volatile AHs can be directly detected down to ng/L levels on a minute time scale. The approach thus may pave the way to future ship application in marine sciences, natural resources exploration or pollutant and hazard detection.

8.
Chemosphere ; 262: 128327, 2021 Jan.
Article in English | MEDLINE | ID: mdl-33182089

ABSTRACT

The globally used herbicide glyphosate and its metabolite aminomethylphosphonic acid (AMPA) have not yet been reported to occur in the marine environment, presumably due to a lack of suitable analytical methods. In this study, we developed two new methods for the analysis of glyphosate and AMPA in seawater: a small-scale method, which includes an SPE cleanup step that minimizes salt-matrix effects during LC-MS/MS analysis, and a large-scale method that employs an additional SPE preconcentration step. Different SPE materials were evaluated for their suitability to enrich glyphosate and AMPA from saltwater and a molecularly imprinted polymer was selected. Both methods were validated in ultrapure water and environmental seawater. Achieved limits of detection with the small-scale method were 6 and 8 ng/L for glyphosate and AMPA, while the large-scale method achieved 0.12 and 0.22 ng/L, respectively. The small-scale method was used to analyze environmental samples from the Warnow Estuary in Germany. Glyphosate and AMPA could be successfully detected in the samples, but could not be measured beyond the saline estuary due to dilution and degradation effects. A set of samples from the western Baltic Sea was analyzed with the large-scale method. Glyphosate and AMPA could be detected in all Baltic Sea samples, especially at stations close to estuaries. To the best of our knowledge, this is the first report on the occurrence of glyphosate and AMPA in seawater.


Subject(s)
Environmental Monitoring/methods , Glycine/analogs & derivatives , Herbicides/analysis , Organophosphonates/analysis , Seawater/chemistry , Water Pollutants, Chemical/analysis , Chromatography, Liquid/methods , Estuaries , Germany , Glycine/analysis , Limit of Detection , Oceans and Seas , Tandem Mass Spectrometry/methods , Glyphosate
9.
Mar Pollut Bull ; 160: 111526, 2020 Nov.
Article in English | MEDLINE | ID: mdl-32836192

ABSTRACT

We report on Baltic Sea polycyclic aromatic hydrocarbon (PAH) pressure based on the U.S. EPA PAHs in view of millennial and decadal developments utilizing data from sediment deposits and seawater. Pre-industrial PAH contents ranged from 500 to 4500 ng/g TOC. Maximum PAH contents were up to 100,000 ng/g TOC and date back to the 1960s to 1970s with maximum pollutant inputs. Contemporary sediment PAH contents with 10,000 to 35,000 ng/g TOC and seawater concentrations with about 1 to 16 ng/l show spatial variability due to different local inputs and sediment characteristics. Pre-industrial compositional change from low molecular weight to high molecular weight (HMW) PAH indicates changing sources from mostly petroleum to combustion. Application of diagnostic ratios reveals petroleum and combustion as contemporary PAH sources and that traffic emissions continuously contribute to the Baltic PAH profile. Medium to high toxicological risk to the marine community might arise from current HMW PAH contents.


Subject(s)
Petroleum , Polycyclic Aromatic Hydrocarbons , Water Pollutants, Chemical , Environmental Monitoring , Geologic Sediments , Industrial Development , Petroleum/analysis , Polycyclic Aromatic Hydrocarbons/analysis , Water Pollutants, Chemical/analysis
10.
Talanta ; 211: 120724, 2020 May 01.
Article in English | MEDLINE | ID: mdl-32070570

ABSTRACT

Methylphosphonic acid (MPn) is suspected to play an important role in aquatic systems like rivers or the open ocean. To gain more insights into the importance of MPn, e.g., for the aquatic phosphorus cycle, an analytical method for its quantitative determination was developed. The method is based on the use of an isotopically-labelled internal standard and sample preparation including solid-phase extraction (SPE). Instrumental detection was done using GC-MS after derivatisation of MPn with N-tert-Butyldimethylsilyl-N-methyltrifluoroacetamide (MTBSTFA). The study compares different isotopically-labelled compounds as well as different SPE-materials. As water samples with high salt content decrease the recovery of the chosen SPE-material, a desalting procedure using electrodialysis was implemented. Finally, water samples from different aquatic systems located at the German Baltic Sea coastal area were analysed to gain first insights into the relevance of MPn in these systems. MPn-concentrations in the low µg/L-range were detected.

11.
Environ Monit Assess ; 192(2): 127, 2020 Jan 21.
Article in English | MEDLINE | ID: mdl-31960150

ABSTRACT

Glyphosate (GLYP), the globally most important herbicide, may have effects in various compartments of the environment such as soil and water. Although laboratory studies showed fast microbial degradation and a low leaching potential, it is often detected in various environmental compartments, but pathways are unknown. Therefore, the objective was to study GLYP leaching and transformations in a lysimeter field experiment over a study period of one hydrological year using non-radioactive 13C2-15N-GLYP labelling and maize cultivation. 15N and 13C were selectively measured using isotopic ratio mass spectrometry (IR-MS) in leachates, soil, and plant material. Additionally, HPLC coupled to tandem mass spectrometry (HPLC-MS/MS) was used for quantitation of GLYP and its main degradation product aminomethylphosphonic acid (AMPA) in different environmental compartments (leachates and soil). Results show low recoveries for GLYP (< 3%) and AMPA (< level of detection) in soil after the study period, whereas recoveries of 15N (11-19%) and 13C (23-54%) were higher. Time independent enrichment of 15N and 13C and the absence of GLYP and AMPA in leachates indicated further degradation. 15N was enriched in all compartments of maize plants (roots, shoots, and cobs). 13C was only enriched in roots. Results confirmed rapid degradation to further degradation products, e.g., 15NH4+, which plausibly was taken up as nutrient by plants. Due to the discrepancy of low GLYP and AMPA concentrations in soil, but higher values for 15N and 13C after the study period, it cannot be excluded that non-extractable residues of GLYP remained and accumulated in soil.


Subject(s)
Environmental Monitoring , Glycine/analogs & derivatives , Soil Pollutants/analysis , Water Pollutants, Chemical/analysis , Chromatography, High Pressure Liquid/methods , Glycine/chemistry , Herbicides/analysis , Isoxazoles , Soil/chemistry , Tandem Mass Spectrometry , Tetrazoles , Water/analysis , Zea mays/metabolism , Glyphosate
12.
Harmful Algae ; 85: 101626, 2019 05.
Article in English | MEDLINE | ID: mdl-31810531

ABSTRACT

The Benguela Current in the Atlantic is one of the four major upwelling systems on the Eastern boundary of the world ocean. Thus the coastal regions off Namibia are prone to high primary productivity that can lead to Harmful Algae Blooms as this nutrient rich water reaches the euphotic zone. Yessotoxins (YTXs) produced by G. spinifera were detected in Namibian phytoplankton field samples in 2011. Isolation of G. spinifera cultures from this location in 2012 enabled molecular genetics work and further liquid chromatography-mass spectrometry assessment of toxin profiles. The molecular work grouped the Benguela G. spinifera with other toxic G. spinifera strains originating from Italy and New Zealand. The main YTX analogs present in the Benguela G. spinifera are homo-YTX, YTX and a hydroxylated analogue. This work adds important knowledge on the occurrence of Harmful Algae Blooms in this region and is of relevance for safety.


Subject(s)
Dinoflagellida , Italy , Mollusk Venoms , Namibia , New Zealand , Oxocins , Phylogeny
13.
Anal Chem ; 91(24): 15547-15554, 2019 12 17.
Article in English | MEDLINE | ID: mdl-31735029

ABSTRACT

The development of sensitive analytical techniques for the real-time detection of aromatic hydrocarbons (AHs) and polycyclic aromatic hydrocarbons (PAHs) is of high importance, because of their impact on human health and the environment. A promising approach, regarding to direct determination of (P)AHs in aqueous samples, is resonance-enhanced multiphoton ionization (REMPI) coupled to external-membrane introduction mass spectrometry (eMIMS). In eMIMS, analytes are extracted from the water phase into the gas phase, which is supplied to the MS by using an external semipermeable membrane setup. As a result, no laborious enrichment techniques are needed. With REMPI, ions are formed by the subsequent absorption of two photons via an excited molecular state. The unique ionization scheme of REMPI provides selective and sensitive detection of (P)AHs. When combining the capabilities of REMPI and MIMS, direct measurements of sub-µg/L concentrations of small (polycyclic)aromatic compounds are feasible. In this study, we present an external sheet membrane probe (ESMP) for the determination of selected (polycyclic)aromatic species in water samples by using REMPI time-of-flight mass spectrometry (REMPI-TOFMS). This inlet design shows promising results with respect to the direct analysis of (P)AHs in aquatic environments. With this early stage system, concentrations down to tens of ng/L for selected small (polycyclic)aromatic compounds are accessible within minutes without any sample preparation.

14.
Ecol Evol ; 9(17): 9916-9934, 2019 Sep.
Article in English | MEDLINE | ID: mdl-31534704

ABSTRACT

Increasing sea surface temperatures (SST) and blooms of lipid-poor, filamentous cyanobacteria can change mesozooplankton metabolism and foraging strategies in marine systems. Lipid shortage and imbalanced diet may challenge the build-up of energy pools of lipids and proteins, and access to essential fatty acids (FAs) and amino acids (AAs) by copepods. The impact of cyanobacterial blooms on individual energy pools was assessed for key species temperate Temora longicornis and boreal Pseudo-/Paracalanus spp. that dominated field mesozooplankton communities isolated by seasonal stratification in the central Baltic Sea during the hot and the cold summer. We looked at (a) total lipid and protein levels, (b) FA trophic markers and AA composition, and (c) compound-specific stable carbon isotopes (δ13C) in bulk mesozooplankton and in a subset of parameters in particulate organic matter. Despite lipid-poor cyanobacterial blooms, the key species were largely able to cover both energy pools, yet a tendency of lipid reduction was observed in surface animals. Omni- and carnivory feeding modes, FA trophic makers, and δ13C patterns in essential compounds emphasized that cyanobacterial FAs and AAs have been incorporated into mesozooplankton mainly via feeding on mixo- and heterotrophic (dino-) flagellates and detrital complexes during summer. Foraging for essential highly unsaturated FAs from (dino-) flagellates may have caused night migration of Pseudo-/Paracalanus spp. from the deep subhalocline waters into the upper waters. Only in the hot summer (SST>19.0°C) was T. longicornis submerged in the colder subthermocline water (~4°C). Thus, the continuous warming trend and simultaneous feeding can eventually lead to competition on the preferred diet by key copepod species below the thermocline in stratified systems. A comparison of δ13C patterns of essential AAs in surface mesozooplankton across sub-basins of low and high cyanobacterial biomasses revealed the potential of δ13C-AA isoscapes for studies of commercial fish feeding trails across the Baltic Sea food webs.

15.
Glob Chang Biol ; 25(3): 794-810, 2019 03.
Article in English | MEDLINE | ID: mdl-30628151

ABSTRACT

Changes in the complexity of planktonic food webs may be expected in future aquatic systems due to increases in sea surface temperature and an enhanced stratification of the water column. Under these conditions, the growth of unpalatable, filamentous, N2 -fixing cyanobacterial blooms, and their effect on planktonic food webs will become increasingly important. The planktonic food web structure in aquatic ecosystems at times of filamentous cyanobacterial blooms is currently unresolved, with discordant lines of evidence suggesting that herbivores dominate the mesozooplankton or that mesozooplankton organisms are mainly carnivorous. Here, we use a set of proxies derived from amino acid nitrogen stable isotopes from two mesozooplankton size fractions to identify changes in the nitrogen source and the planktonic food web structure across different microplankton communities. A transition from herbivory to carnivory in mesozooplankton between more eutrophic, near-coastal sites and more oligotrophic, offshore sites was accompanied by an increasing diversity of microplankton communities with aging filamentous cyanobacterial blooms. Our analyses of 124 biotic and abiotic variables using multivariate statistics confirmed salinity as a major driver for the biomass distribution of non-N2 -fixing microplankton species such as dinoflagellates. However, we provide strong evidence that stratification, N2 fixation, and the stage of the cyanobacterial blooms regulated much of the microplankton diversity and the mean trophic position and size of the metabolic nitrogen pool in mesozooplankton. Our empirical, macroscale data set consistently unifies contrasting results of the dominant feeding mode in mesozooplankton during blooms of unpalatable, filamentous, N2 -fixing cyanobacteria by identifying the at times important role of heterotrophic microbial food webs. Thus, carnivory, rather than herbivory, dominates in mesozooplankton during aging and decaying cyanobacterial blooms with hitherto uncharacterized consequences for the biogeochemical functions of mesozooplankton.


Subject(s)
Cyanobacteria/physiology , Eutrophication , Food Chain , Nitrogen Fixation , Plankton/physiology , Biomass , Cyanobacteria/metabolism , Ecosystem , Nitrogen/metabolism , Nitrogen Isotopes/metabolism , Plankton/classification , Plankton/metabolism , Salinity
16.
Mar Pollut Bull ; 137: 668-676, 2018 Dec.
Article in English | MEDLINE | ID: mdl-30503482

ABSTRACT

We investigated the concentration distribution and composition of organic pollutants in sediments of the shelf and the deep northern South China Sea (NSCS). Concentrations of polycyclic aromatic hydrocarbons (Σ15PAH; 10.69-66.45 ng g-1), Dichlorodiphenyltrichloroethane (Σ4DDT; 0-0.82 ng g-1), and polychlorinated biphenyls (Σ24PCB; 0-0.12 ng g-1) are below established sediment quality guidelines, suggesting no environmental risk. Surprisingly, concentrations increase from the shelf to the deep NSCS, and are higher in the east of the study area. The organic pollutant composition indicates PAH mainly derived from pyrogenic sources, and mostly degraded DDT and PCB. However, in the deep NSCS, considerable contribution of petrogenic PAH, low chlorinated PCB and p,p'-DDT suggest more recent input from different sources compared to the shelf. From these results we infer that organic pollution in the NSCS does not originate from the Pearl River Estuary but from the NE SCS, SW of Taiwan.


Subject(s)
Geologic Sediments/analysis , Hydrocarbons, Chlorinated/analysis , Polycyclic Aromatic Hydrocarbons/analysis , Water Pollutants, Chemical/analysis
17.
Talanta ; 188: 192-198, 2018 Oct 01.
Article in English | MEDLINE | ID: mdl-30029363

ABSTRACT

Several key aspects for the analysis of inositol hexakisphosphate (InsP6) have been investigated in order to establish a suitable method for the study of sediment samples from different aquatic systems. Apparent matrix effects for the ion chromatography electrospray ionization tandem mass spectrometric detection (IC-ESI-MS/MS) method were accounted for with a standard addition approach, which also compensated for variation in extraction efficiency. Several parameters of the extraction method were optimized to improve the extraction efficiency for different sediment types. We observed an improvement in the extraction efficiency between 18% and 720%. Finally, the method was used to gain first insights into the relevance of InsP6 in two aquatic systems located at the German Baltic coastal area. InsP6 was detected in several sediment samples with concentrations between 2.3 and 15.2 µg InsP6-P/g dry weight (DW).

18.
Sci Total Environ ; 613-614: 557-568, 2018 Feb 01.
Article in English | MEDLINE | ID: mdl-28926810

ABSTRACT

With the increase in anthropogenic environmental disruption, the behavior of arsenic in the Baltic Sea has received more scientific attention because of its complex forms and toxicity, and was re-visited to determine if there have been measurable changes recently. A cruise was conducted in 10-19 May 2011 to investigate the species and distribution of total dissolved inorganic arsenic (TDIAs: [TDIAs]=[As(V)]+[As(III)]) revealing links between the hydrographic dynamics and biological/chemical reactions in the Baltic Sea. In addition, long-term (2002-2010) time-series investigations of particulate arsenic in the Gotland Basin were also conducted in February every year for monitoring purposes. The behavior of TDIAs was non-conservative due to the removal and regeneration processes occurring in the Baltic Sea. Biological scavenging plays a dominant role as sink for TDIAs, with removal amount of 3.1±1.6nmol/L above the pycnocline of the Baltic Sea. Significant regeneration of TDIAs was observed below the pycnocline of the Baltic Sea, which was closely related to hypoxia. The decomposition of organic arsenic and release from the sediment by desorption of As-bearing Fe and Mn oxides were thought to be two major sources for TDIAs regeneration. The median concentration of TDIAs (8.4nmol/L) was much lower than in most marginal seas and oceans, including the near-bottom water around a chemical weapon dumpsite (13.9nmol/L). The hypoxia in the deep water contributed to the increase in As(III) concentrations based on the relationship between As(III)/TDIAs ratio and apparent oxygen utilization. If the difference of As(III) profiles (1981 and 2011) actually represents a long-term increase in As(III) concentrations and a shoaling of the As(III) chemocline, these factors could enhance the toxic effects and extend the residence time of arsenic and, hence, potentially have negative impacts on fisheries and ecosystem health in the Baltic Sea.

19.
Chemosphere ; 191: 886-894, 2018 Jan.
Article in English | MEDLINE | ID: mdl-29107230

ABSTRACT

Sediment cores and bottom water samples from across the Baltic Sea region were analyzed for freely dissolved concentrations (Cfree), total sediment concentrations (CT) and the dissolved aqueous fraction in water of seven indicator PCBs. Ex-situ equilibrium sampling of sediment samples was conducted with polydimethylsiloxane (PDMS) coated glass fibers that were analyzed by automated thermal desorption GC-MS, which yielded PCB concentrations in the fiber coating (CPDMS). Measurements of CPDMS and CT were then applied to determine (i) spatially resolved freely dissolved PCB concentrations; (ii) baseline toxicity potential based on chemical activities (a); (iii) site specific mixture compositions; (iv) diffusion gradients at the sediment water interface and within the sediment cores; and (vi) site specific distribution ratios (KD). The contamination levels were low in the Gulf of Finland and moderate to elevated in the Baltic Proper, with the highest levels observed in the western Baltic Sea. The SPME method has been demonstrated to be an appropriate and sensitive tool for area surveys presenting new opportunities to study the in-situ distribution and thermodynamics of hydrophobic organic chemicals at trace levels in marine environments.


Subject(s)
Environmental Monitoring/methods , Polychlorinated Biphenyls/analysis , Seawater/chemistry , Water Pollutants, Chemical/analysis , Environmental Pollution/analysis , Finland , Gas Chromatography-Mass Spectrometry , Geologic Sediments/chemistry , Organic Chemicals/analysis
20.
Environ Sci Technol ; 51(20): 11692-11700, 2017 Oct 17.
Article in English | MEDLINE | ID: mdl-28885012

ABSTRACT

The Baltic Sea is a marginal sea characterized by stagnation periods of several years. Oxygen consumption in its deep waters leads to the buildup of sulfide from sulfate reduction. Some of the microorganisms responsible for these processes also transform reactive ionic mercury to neurotoxic methylmercury. Episodic inflows of oxygenated saline water from the North Sea temporally re-establish oxic life in deep waters of the Baltic Sea. Thus, this sea is an especially important region to better understand mercury species distributions in connection with variable redox conditions. Mercury species were measured on three Baltic Sea campaigns, during the preinflow, ongoing inflow, and subsiding inflow of water, respectively, to the central basin. The inflowing water caused the removal of total mercury by 600 nmol m-2 and of methylmercury by 214 nmol m-2 in the Gotland Deep, probably via attachment of the mercury compounds to sinking particles. It appears likely that the consequences of the oxygenation of Baltic Sea deep waters, which are the coprecipitation of mercury species and the resettlement of the oxic deep waters, could lead to the enhanced transfer of accumulated mercury and methylmercury to the planktonic food chain and finally to fish.


Subject(s)
Methylmercury Compounds , Seawater , Animals , Baltic States , Mercury , North Sea
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