Aerosol emissions from a marine diesel engine running on different fuels and effects of exhaust gas cleaning measures.

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.

Substances of emerging concern in Baltic Sea water: Review on methodological advances for the environmental assessment and proposal for future monitoring.

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.

Biomarker-based assessment of sublethal toxicity of organic UV filters (ensulizole and octocrylene) in a sentinel marine bivalve Mytilus edulis.

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.

Seasonal variability, long-term distribution (2001-2014), and risk assessment of polar organic micropollutants in the Baltic Sea.

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.

The challenge of detecting the herbicide glyphosate and its metabolite AMPA in seawater - Method development and application in the Baltic Sea.

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.

Polycyclic aromatic hydrocarbons in the Baltic Sea - Pre-industrial and industrial developments as well as current status.

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.

Methodological aspects of methylphosphonic acid analysis: Determination in river and coastal water samples.

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.

Leaching and degradation of 13C2-15N-glyphosate in field lysimeters.

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.

Phylogenetic analysis and yessotoxin profiles of Gonyaulax spinifera cultures from the Benguela Current upwelling system.

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.

Polycyclic and organochlorine hydrocarbons in sediments of the northern South China Sea.

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.

The Impact of the Major Baltic Inflow of December 2014 on the Mercury Species Distribution in the Baltic Sea.

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.

Occurrence of pharmaceuticals and UV-filters in riverine run-offs and waters of the German Baltic Sea.

The occurrence of pharmaceuticals and personal care products (PPCPs) in the marine environment is of great concern. This study was done to determine the emergence of eight pharmaceuticals and eleven ultraviolet filters (UV-Filters) in 5 rivers/streams discharging into the Baltic Sea. Furthermore, a focus was put on the influence of wastewater treatment plant as indirect source and the occurrence of the PPCPs in close beach proximity. Two pharmaceuticals (sulfamethoxazole, salicylic acid) and two UV-filters (2-phenylbenzimidazole-5-sulfonic acid, octocrylene) were detected in all analyzed water samples, with concentration ranging from 0.6ng/L to 836.3ng/L. In all rivers the PPCP concentration decreases towards the Baltic Sea. Sulfamethoxazole was detected at comparable concentration along the coast, which leads to the assumption of stable concentration in beach proximity. Along the coast UV-filters appeared in varying concentrations, leading to the conclusion that the direct input into the marine environment plays a bigger role than the indirect input.

Methods comparison, transport and distribution of polar herbicides in the Baltic Sea.

Two LC-MS/MS methods including different sample preparation and quantitative processes showed a good agreement for analysis of the herbicides MCPA, mecoprop, isoproturon, bentazon and chloridazon, and the metabolite chloridazon-methyl-desphenyl (CMD) in estuarine waters. Due to different sensitivity of the methods only one could be used to analyze marine samples. The transport of these compounds to the Baltic Sea via ten German estuaries and their distribution between coastal water and sediments was studied. The results showed that all selected compounds can be transported to the Baltic Sea (0.9-747ng/L). Chloridazon, bentazon, isoproturon and CMD were detected (0.9-8.9ng/L) in the coastal waters and chloridazon and isorproturon in the sediments (5-136pg/g d.w.). Levels of contaminants in the sediments could be influenced by the total organic carbon content. Concentrations observed in the Baltic Sea are most likely not high enough to cause acute effects, but long term effect studies are strongly recommended.

A Multi-Pumping Flow System for In Situ Measurements of Dissolved Manganese in Aquatic Systems.

A METals In Situ analyzer (METIS) has been used to determine dissolved manganese (II) concentrations in the subhalocline waters of the Gotland Deep (central Baltic Sea). High-resolution in situ measurements of total dissolved Mn were obtained in near real-time by spectrophotometry using 1-(2-pyridylazo)-2-naphthol (PAN). PAN is a complexing agent of dissolved Mn and forms a wine-red complex with a maximum absorbance at a wavelength of 562 nm. Results are presented together with ancillary temperature, salinity, and dissolved O 2 data. Lab calibration of the analyzer was performed in a pressure testing tank. A detection limit of 77 nM was obtained. For validation purposes, discrete water samples were taken by using a pump-CTD system. Dissolved Mn in these samples was determined by an independent laboratory based method (inductively coupled plasma-optical emission spectrometry, ICP-OES). Mn measurements from both METIS and ICP-OES analysis were in good agreement. The results showed that the in situ analysis of dissolved Mn is a powerful technique reducing dependencies on heavy and expensive equipment (pump-CTD system, ICP-OES) and is also cost and time effective.

The influence of salt matrices on the reversed-phase liquid chromatography behavior and electrospray ionization tandem mass spectrometry detection of glyphosate, glufosinate, aminomethylphosphonic acid and 2-aminoethylphosphonic acid in water.

The analysis of highly polar and amphoteric compounds in seawater is a continuing challenge in analytical chemistry due to the possible formation of complexes with the metal cations present in salt-based matrices. Here we provide information for the development of analytical methods for glyphosate, glufosinate, AMPA, and 2-AEP in salt water, based on studies of the effects of salt matrices on reversed-phase liquid chromatography-heated electrospray ionization-tandem mass spectrometry (RP-LC-HESI-MS/MS) after derivatization of the target compounds with FMOC-Cl. The results showed that glyphosate was the only analyte with a strong tendency to form glyphosate-metal complexes (GMC), which clearly influenced the analysis. The retention times (RTs) of GMC and free glyphosate differed by approximately 7.00min, reflecting their distinct RP-LC behaviors. Divalent cations, but not monovalent (Na+, K+) or trivalent (Al3+, Fe3+) cations, contributed to this effect and their influence was concentration-dependent. In addition, Cu2+, Co2+, Zn2+, and Mn2+ prevented glyphosate detection whereas Ca2+, Mg2+, and Sr2+ altered the retention time. At certain tested concentrations of Ca2+ and Sr2+ glyphosate yielded two peaks, which violated the fundamental rule of LC, that under the same analytical conditions a single substance yields only one LC-peak with a specific RT. Salt-matrix-induced ion suppression was observed for all analytes, especially under high salt concentrations. For glyphosate and AMPA, the use of isotopically labeled internal standards well-corrected the salt-matrix effects, with better results achieved for glufosinate and 2-AEP with the AMPA internal standard than with the glyphosate internal standard. Thus, our study demonstrated that Ca2+, Mg2+, and Sr2+ can be used together with FMOC-Cl to form GMC-FMOC which is suitable for RP-LC-HESI-MS/MS analysis.

Profiles and inventories of organic pollutants in sediments from the central Beibu Gulf and its coastal mangroves.

Sediment cores from the central Beibu Gulf and its northern coastal mangroves were analyzed for polycyclic aromatic hydrocarbons (PAH), the organo-chlorine pesticides dichlorodiphenyltrichloroethane (DDT) and hexachlorobenzene (HCB), and polychlorinated biphenyls (PCB), to reconstruct the organic pollution history of developing south-west China. Reflecting regional development, in the gulf ∑PAH (38-74 ng g(-1)) decreased towards the surface after peak concentrations near 10 cm, while ∑DDT (ND - 0.5 ng g(-1)) increased due to fresh inputs, and HCB (ND - 0.04 ng g(-1)) occurred only in surface sediments. Profiles in mangrove sediments showed a continuing local scale increase in ∑PAH (29-438 ng g(-1)) as well as ∑DDT (0.2-41.0 ng g(-1)) and HCB (0.01-1.01 ng g(-1)) pollution, despite some variability. No trend was evident for ∑PCB (ND - 0.22 ng g(-1)), which was not detected in the central gulf. Calculated loads estimate that 2816 ng cm(-2) PAHs and 7 ng cm(-2) DDTs are stored in depositional areas of the Beibu Gulf. Mangrove sediments, threatened by land-use-change, contain 1400-4600 ng cm(-2) PAHs and 34-39 ng cm(-2) DDTs.

Organic pollutants in the central and coastal Beibu Gulf, South China Sea.

Surface sediments from the central and coastal Beibu Gulf, southern China, were analyzed for persistent organic pollutants. The absence of polychlorinated biphenyls (PCB; generally below detection limit), low concentrations of polycyclic aromatic hydrocarbons (PAH; 24-647 ng g(-1)), and locally high contamination with organo-chloro pesticides (DDT; 0.03-92 ng g(-1)) reflect the early stages of development in southwest China, with human activities dominated by agriculture and low impact of industry. Concentrations of PCB and PAH indicate no ecological risk, while DDT accumulation poses a probable toxic risk in coastal but not in shelf sediments. Diagnostic ratios suggest PAH originating mainly from combustion of biomass and diesel fuels, and recent DDT use in agriculture and antifouling paint. Distribution patterns along the coastal-shelf-gradient indicate mainly airborne transport of PAH and waterborne transport of DDT. In the central Gulf, also water column samples reveal low concentrations of PAH (1.7-7.8 ng L(-1)) and DDT (0.006-0.053 ng L(-1)).

Organic polar pollutants in surface waters of inland seas.

Available data about contamination by polar substances are mostly reported for rivers and near-shore waters and only limited studies exists about their occurrence in marine waters. We present concentrations and distribution of several polar pesticides and UV-filters in surface waters of three inland seas, the Baltic, Black and Mediterranean Sea. Many of the investigated compounds were below detection limits, however, those found in off-shore waters raise a concern about their persistence and possible adverse effect on the ecosystem. Despite a longstanding EU-wide ban we were able to detect atrazine in the Mediterranean and the Baltic Sea. Concentrations in the Black Sea were substantially higher. Runoff from agricultural and urban areas was the main transport route to marine ecosystems for investigated compounds, though irgarol in Mediterranean waters was attributed to intense maritime traffic. 2-Phenylbenzimidazole-5-sulfonic acid was the only UV-filter detected in marine waters, while benzophenone-4 was observed in the estuaries. Occurrence of UV-filters was seasonal.

Glyphosate and AMPA in the estuaries of the Baltic Sea method optimization and field study.

Water samples from ten German Baltic estuaries were collected in 2012 in order to study the presence of the herbicide glyphosate, its primary metabolite AMPA and their potential transport to the marine environment. For the analyses an LC-MS/MS based analytical method after derivatization with FMOC-Cl was optimized and validated for marine water samples. All investigated estuarine stations were contaminated with AMPA and nine of them also with glyphosate. Concentration ranges observed were 28 to 1690ng/L and 45 to 4156ng/L for glyphosate and AMPA, respectively with strong spatial and temporal fluctuations. Both contaminants were found at inbound sampling sites in the stream Muehlenfliess and concentrations decreased along the salinity gradient to the estuaries of the Baltic Sea. The data obtained in this study clearly depict the transport of glyphosate and AMPA to the Baltic Sea. Hence, detailed fate and risk assessment for both contaminants in marine environments are required.