Arsenic speciation in low-trophic marine food chain - An arsenic exposure study on microalgae (Diacronema lutheri) and blue mussels (Mytilus edulis L.).

Microalgae and blue mussels are known to accumulate undesirable substances from the environment, including arsenic (As). Microalgae can biotransform inorganic As (iAs) to organoarsenic species, which can be transferred to blue mussels. Knowledge on As uptake, biotransformation, and trophic transfer is important with regards to feed and food safety since As species have varying toxicities. In the current work, experiments were conducted in two parts: (1) exposure of the microalgae Diacronema lutheri to 5 and 10 µg/L As(V) in seawater for 4 days, and (2) dietary As exposure where blue mussels (Mytilus edulis L.) were fed with D. lutheri exposed to 5 and 10 µg/L As(V), or by aquatic exposure to 5 µg/L As(V) in seawater, for a total of 25 days. The results showed that D. lutheri can take up As from seawater and transform it to methylated As species and arsenosugars (AsSug). However, exposure to 10 µg/L As(V) resulted in accumulation of iAs in D. lutheri and lower production of methylated As species, which may suggest that detoxification mechanisms were overwhelmed. Blue mussels exposed to As via the diet and seawater showed no accumulation of As. Use of linear mixed models revealed that the blue mussels were gradually losing As instead, which may be due to As concentration differences in the mussels' natural environment and the experimental setup. Both D. lutheri and blue mussels contained notable proportions of simple methylated As species and AsSug. Arsenobetaine (AB) was not detected in D. lutheri but present in minor fraction in mussels. The findings suggest that low-trophic marine organisms mainly contain methylated As species and AsSug. The use of low-trophic marine organisms as feed ingredients requires further studies since AsSug are regarded as potentially toxic, which may introduce new risks to feed and food safety.

Micropollutants in urban wastewater: large-scale emission estimates and analysis of measured concentrations in the Baltic Sea catchment.

Wastewater treatment plants (WWTPs) transmit many chemical contaminants to aquatic environments. Quantitative data on micropollutant emissions via WWTPs are needed for environmental risk assessments and evaluation of mitigation measures. This study compiled published data on substances analysed in effluents from WWTPs in the Baltic Sea region, assessed country related differences in the data sets and estimated micropollutant inputs to the Baltic Sea catchment. Concentration data were found for 1090 substances analysed at 650 WWTPs. Heterogeneity and low number of data points for most substances hindered adequate comparisons of country specific concentrations. Emission estimates were made for the 280 substances analysed in at least five WWTPs in years 2010 to 2019. For selected substances, mass loads were compared to previously published estimations. The study provides data useful for national and Baltic Sea-scale pressure analysis and risk assessments. However, it also highlights the need for broad scope monitoring of micropollutants in wastewater.

A risk assessment review of mercury exposure in Arctic marine and terrestrial mammals.

There has been a considerable number of reports on Hg concentrations in Arctic mammals since the last Arctic Monitoring and Assessment Programme (AMAP) effort to review biological effects of the exposure to mercury (Hg) in Arctic biota in 2010 and 2018. Here, we provide an update on the state of the knowledge of health risk associated with Hg concentrations in Arctic marine and terrestrial mammal species. Using available population-specific data post-2000, our ultimate goal is to provide an updated evidence-based estimate of the risk for adverse health effects from Hg exposure in Arctic mammal species at the individual and population level. Tissue residues of Hg in 13 species across the Arctic were classified into five risk categories (from No risk to Severe risk) based on critical tissue concentrations derived from experimental studies on harp seals and mink. Exposure to Hg lead to low or no risk for health effects in most populations of marine and terrestrial mammals, however, subpopulations of polar bears, pilot whales, narwhals, beluga and hooded seals are highly exposed in geographic hotspots raising concern for Hg-induced toxicological effects. About 6% of a total of 3500 individuals, across different marine mammal species, age groups and regions, are at high or severe risk of health effects from Hg exposure. The corresponding figure for the 12 terrestrial species, regions and age groups was as low as 0.3% of a total of 731 individuals analyzed for their Hg loads. Temporal analyses indicated that the proportion of polar bears at low or moderate risk has increased in East/West Greenland and Western Hudson Bay, respectively. However, there remain numerous knowledge gaps to improve risk assessments of Hg exposure in Arctic mammalian species, including the establishment of improved concentration thresholds and upscaling to the assessment of population-level effects.

Seasonal rainfall affects occurrence of organohalogen contaminants in tropical marine fishes and prawns from Zanzibar, Tanzania.

Seasonal differences in precipitation may affect contaminant dynamics in tropical coastal regions due to terrestrial runoff of contaminants to the marine environment after the rainy seasons. To assess the effect of seasonal rainfall on occurrence of organohalogen contaminants in a coastal ecosystem, marine fishes and prawns were collected off the coast of Zanzibar, Tanzania in January and August 2018, representing pre- and post-rainy season, respectively. Samples were analyzed for organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), brominated flame retardants (BFRs), including polybrominated diphenyl ethers (PBDEs) and emerging BFRs, as well as the dietary descriptors stable isotopes of carbon (δ13C) and nitrogen (δ15N). Across all species and seasons, mean contaminant concentrations ranged from below limit of detection (LOD) to 129 ng/g lipid weight (lw) ΣPCBs; 5.6-336 ng/g lw ΣOCPs; and < LOD -22.1 ng/g lw ΣPBDEs. Most of the emerging BFRs were below LOD. Contaminant concentrations generally increased with higher pelagic carbon signal (δ13C) and higher relative trophic position (δ15N). The ratio of DDE/ΣDDTs in fishes and prawns was lower in August than in January, suggesting runoff of non-degraded DDT into the marine system during or after the seasonal rainfall. Contaminant patterns of OCPs and PCBs, and concentrations of BFRs, differed between seasons in all species. A higher relative concentration-increase in lower halogenated, more mobile PCB and PBDE congeners, compared to higher halogenated congeners with lower mobility, between January and August aligns with a signal and effect of terrestrial runoff following the rainy season.

Persistent organic pollutants and related biological responses measured in coastal fish using chemical and biological screening methods.

The aim of this study was to investigate the spatial distribution, levels of dioxin-like compounds (DLC), and biological responses in two fish species. The viviparous eelpout (Zoarces viviparus) was collected from various locations in the Baltic Sea and in fjords of Kattegat and Skagerrak, while shorthorn sculpin (Myoxocephalus scorpius) was obtained at the polychlorinated biphenyl (PCB) polluted site in North West Greenland. Significant differences were detected both in contaminant levels and relative contributions from either polychlorinated dibenzodioxins (PCDD) or polychlorinated dibenzofurans (PCDF or furans) and mono-ortho- and non-ortho (coplanar) polychlorinated biphenyls (dl-PCB). Fish from the eastern Baltic Sea generally displayed higher contributions from PCDD/F compared to dl-PCB, whereas dl-PCB were generally predominated in fish from Danish, Swedish, and German sites. Levels of dl-PCB in muscle tissues were above OSPAR environmental assessment criteria (EAC) for PCB118, indicating a potential risk of adverse biological effects in the ecosystem, whereas levels of the total WHO-TEQs were below threshold for sea food suggesting limited risks for humans. No significant relationships between levels of DLC (expressed as WHO-TEQ), and biological responses such as the induction of CYP1A enzymatic activity and fry reproductive disorders were observed in eelpout. No marked relationship between WHO-TEQ and combined biological aryl hydrocarbon receptor-mediated transactivity (expressed as AhR-TEQ) was noted. However, there was a positive correlation between polycyclic aromatic hydrocarbon (PAH) metabolites and induction of CYP1A activity, suggesting that PAH exhibited greater potential than DLC to produce biological effects in eelpout from the Baltic Sea.

Development and testing of a prototype tool for integrated assessment of chemical status in marine environments.

We report the development and application of a prototype tool for integrated assessment of chemical status in aquatic environments based on substance- and matrix-specific environmental assessment criteria (thresholds). The Chemical Status Assessment Tool (CHASE) integrates data on hazardous substances in water, sediments and biota as well as bio-effect indicators and is based on a substance- or bio-effect-specific calculation of a 'contamination ratio' being the ratio between an observed concentration and a threshold value. Values <1.0 indicate areas potentially 'unaffected', while values >1.0 indicate areas potentially 'affected'. These ratios are combined within matrices, i.e. for water, sediment and biota and for biological effects. The overall assessment used a 'one out, all out principle' with regard to each matrix. The CHASE tool was tested in the Baltic Sea and the North Sea in 376 assessment units. In the former, the chemical status was >1.0 in practically all areas indicating that all areas assessed were potentially affected. The North Sea included areas classified as unaffected or affected. The CHASE tool can in combination with temporal trend assessments of individual substances be advantageous for use in remedial action plans and, in particular, for the science-based evaluation of the status and for determining which specific substances are responsible for a status as potentially affected.

Passive Sampling in Regulatory Chemical Monitoring of Nonpolar Organic Compounds in the Aquatic Environment.

We reviewed compliance monitoring requirements in the European Union, the United States, and the Oslo-Paris Convention for the protection of the marine environment of the North-East Atlantic, and evaluated if these are met by passive sampling methods for nonpolar compounds. The strengths and shortcomings of passive sampling are assessed for water, sediments, and biota. Passive water sampling is a suitable technique for measuring concentrations of freely dissolved compounds. This method yields results that are incompatible with the EU's quality standard definition in terms of total concentrations in water, but this definition has little scientific basis. Insufficient quality control is a present weakness of passive sampling in water. Laboratory performance studies and the development of standardized methods are needed to improve data quality and to encourage the use of passive sampling by commercial laboratories and monitoring agencies. Successful prediction of bioaccumulation based on passive sampling is well documented for organisms at the lower trophic levels, but requires more research for higher levels. Despite the existence of several knowledge gaps, passive sampling presently is the best available technology for chemical monitoring of nonpolar organic compounds. Key issues to be addressed by scientists and environmental managers are outlined.

Trace elements determination in seawater by ICP-MS with on-line pre-concentration on a Chelex-100 column using a 'standard' instrument setup.

Trace element determination in seawater is analytically challenging due to the typically very low concentrations of the trace elements and the potential interference of the salt matrix. A common way to address the challenge is to pre-concentrate the trace elements on a chelating resin, then rinse the matrix elements from the resin and subsequently elute and detect the trace elements using inductively coupled plasma mass spectrometry (ICP-MS). This technique typically involves time-consuming pre-treatment of the samples for 'off-line' analyses or complicated sample introduction systems involving several pumps and valves for 'on-line' analyses. As an alternative, the following method offers a simple method for 'on-line' analyses of seawater by ICP-MS. As opposed to previous methods, excess seawater was pumped through the nebulizer of the ICP-MS during the pre-concentration step but the gas flow was adjusted so that the seawater was pumped out as waste without being sprayed into the instrument. Advantages of the method include: •Simple and convenient analyses of seawater requiring no changes to the 'standard' sample introduction system except from a resin-filled micro-column connected to the sample tube. The 'standard' sample introduction system refers to that used for routine digest-solution analyses of biota and sediment by ICP-MS using only one peristaltic pump; and•Accurate determination of the elements V, Mn, Co, Ni, Cu, Zn, Cd and Pb in a range of different seawater matrices verified by participation in 6 successive rounds of the international laboratory intercalibration program QUASIMEME.

Mercury exports from a High-Arctic river basin in Northeast Greenland (74°N) largely controlled by glacial lake outburst floods.

Riverine mercury (Hg) export dynamics from the Zackenberg River Basin (ZRB) in Northeast Greenland were studied for the period 2009-2013. Dissolved and sediment-bound Hg was measured regularly in the Zackenberg River throughout the periods with running water (June-October) and coupled to water discharge measurements. Also, a few samples of snow, soil, and permafrost were analysed for Hg. Mean concentrations of dissolved and sediment-bound Hg in the river water (±SD) were 0.39 ± 0.13 and 5.5 ± 1.4 ngL(-1), respectively, and mean concentrations of Hg in the river sediment were 0.033 ± 0.025 mg kg(-1). Temporal variations in river Hg were mainly associated with snowmelt, sudden erosion events, and outburst floods from a glacier-dammed lake in the upper part of the ZRB. Annual Hg exports from the 514 km(2) ZRB varied from 0.71 to >1.57 kg and the majority (86-96%) was associated with sediment-bound Hg. Hg yields from the ZRB varied from 1.4-3.1 gH gk m(-2)yr(-1) and were among the highest yields reported from Arctic river basins. River exports of Hg from ZRB were found to be largely controlled by the frequency, magnitude and timing of the glacial lake outburst floods, which occurred in four of the five years in July-August. Floods accounted for 5 to >10% of the annual water discharge, and up to >31% of the annual Hg export. Also, the winter snowfall and the summer temperatures were found to be important indirect controls on the annual Hg export. The occurrence and timing of glacial lake outburst floods in the ZRB in late summer at the time of maximum soil thaw depth, the location of the glacier in the upper ZRB, and increased thawing of the permafrost in Zackenberg in recent years leading to destabilisation of river banks are considered central factors explaining the high fraction of flood-controlled Hg export in this area.

Sediment baseline study of levels and sources of polycyclic aromatic hydrocarbons and heavy metals in Lake Nicaragua.

Selected metals and polycyclic aromatic hydrocarbons (PAHs) were analyzed in sediment samples from 24 sites in Lake Nicaragua sampled May 2010 to provide a baseline of pollution levels. Cu exceeded the Consensus-Based Sediment Quality Guideline (CBSQG) Threshold Effect Concentrations (TECs) at 21 sites while Ni exceeded the value at one site. Comparison of the sampling sites showed that the south-eastern shore and a central part of the lake contained the highest levels of As, Cd, Cr, and Ni, while the western part of the lake contained the highest levels of Cu, Pb, and Zn. Analysis of PAH levels showed that the CBSQG TECs were exceeded by naphthalene at five sites. The sum concentrations of the 16 US EPA priority PAHs (∑PAH16) ranged from 0.01 mg kg(-1) dw to 0.64 mg kg(-1) dw. The highest ∑PAH16 concentration was found upstream in River Mayales and the PAH composition revealed a heavy PAH fraction (e.g., creosote). The main sources of PAHs in Lake Nicaragua were determined as of diffuse petrogenic and pyrogenic origin as well as diagenetic produced perylene. The relative importance of these PAH sources was determined by interpretation of loading and score plots from a principal component analysis. This study concluded that areas of Lake Nicaragua represent an important pollution baseline for future studies in this lake and other tropical lakes.

Endocrine-disrupting effects of compounds in Danish streams.

Effluents from municipal wastewater-treatment plants and scattered dwellings, as well as runoff from agricultural fields, are sources of endocrine-disrupting compounds (EDCs) in the aquatic environment. The present study investigated the correlation between the occurrence of EDCs in nine Danish streams using passive samplers (polar organic integrative samplers and silicone membranes) and determined their possible biological effects as assessed by mammal cell cultures and the mussel (Unio tumidus). The passive samplers and mussels were exposed simultaneously at the study sites. The extracts from the passive samplers were used to measure the concentrations of EDCs and the biological effects on the estrogen (ER), androgen (AR), and aryl hydrocarbon (AhR)-receptor transactivation. Male mussels were investigated for biomarkers of endocrine effects, such as the levels of vitellogenin-like proteins measured as alkali-labile phosphate (ALP). EDC concentrations, hormone-receptor transactivation (ER, AR, AhR), and level of ALP were greater downstream of wastewater-treatment plants compared with upstream sites and sites supposed to be relatively nonimpacted by wastewater. Furthermore, there was a significant positive correlation between in vitro AhR transactivation and frequency of ALP of male mussels. We conclude that wastewater effluent is an important source of endocrine-disrupting effects in the aquatic environment and that the combination of biological effect measurements and chemical analyses based on passive sampling is useful in the assessment of the ecological state of the aquatic environment.

Occurrence and sorption properties of arsenicals in marine sediments.

The content of total arsenic, the inorganic forms: arsenite (As(III)) and arsenate (As(V)), the methylated forms: monomethylarsonic acid and dimethylarsinic acid (DMA), trimethylarsenic oxide, tetramethylarsenonium ion and arsenobetaine was measured in 95 sediment samples and 11 pore water samples from the Baltic Sea near the island of Bornholm at depths of up to 100 m. As(III+V) and DMA were detected in the sediment and As(III+V) was detected in the sediment pore water. Average total As concentration of 10.6 ± 7.4 mg/kg dry matter (DM) in the sediment corresponds to previously reported values in the Baltic Sea and other parts of the world. Existing data for on-site measurements of sorption coefficients (Kd) of arsenicals in marine and freshwater sediments show large variability from <1 to >1,000 L/kg. In this work, calculated sorption coefficients (Kd and Koc) for As(III+V) showed significant correlation with depth, dissolved oxygen (DO), salinity and sediment classification; for depths <70 m, salinity <11 %, DO >9 mg/L and sand/silt/clay sediments the Kd was 118 ± 76 L/kg DM and for depths >70 m, salinity >11 %, DO < 9 mg/L and muddy sediments the Kd was 513 ± 233 L/kg DM. The authors recommend using the found Kd value for arsenic in marine sediments when conditions are similar to the Baltic Sea. At locations with significant anthropogenic point sources or where the local geology contains volcanic rock and sulphide mineral deposits, there may be significantly elevated arsenic concentrations, and it is recommended to determine on-site Kd values.

Lead isotopes in marine surface sediments reveal historical use of leaded fuel.

Analyses of lead (Pb) isotopes have been performed in terrestrial and fresh water environments to estimate historical uses of leaded fuel, but so far this method has not been employed in studies of world-wide marine surface sediments. We analyzed Pb and its isotopes in 23 surface sediments from four continents collected during the Galathea 3 expedition in 2006-2007. To enhance the anthropogenic signal, a partial digestion using nitric acid was performed. The concentrations of Pb, Th, U and Al were determined with an ICP-Quadrupole MS, and Pb-isotope ratios with an ICP-multi-collector MS. The samples could be divided into three groups: Harbor areas in larger cities with concentrations of 150 to 265 mg kg(-1) dry weight, smaller towns with concentrations between 20 and 40 mg kg(-1) dry weight, and remotely located sites with concentrations below 15 mg kg(-1) dry weight. Pb-isotope ratios were compared to literature values for gasoline and local or geological background values, and the contribution of leaded-gasoline to total concentrations was calculated for contaminated sites using both a one-dimensional and a novel two-dimensional (vector) method. The North American sites had Pb-isotope ratios corresponding to the US leaded gasoline, with 24-88% of the Pb from leaded gasoline. Samples from Oceania showed Pb-isotope ratios corresponding to Australian gasoline, with 60% attributed to leaded gasoline in Sydney and 21% in Christchurch. Outside Cape Town, 15 to 46% of Pb in sediments was from leaded gasoline.

Metals and organotins in multiple bivalve species in a one-off global survey.

The Galathea 3 expedition circumnavigated the globe in 2006-2007 and collected marine samples from six continents. Bivalves were collected from harbours, other impacted locations and reference sites, and samples from 57 sites were analyzed for metals and 47 for organotins, to assess current contamination levels on a global scale. Metal concentrations in nine bivalve species were normalised to the Mytilidae family using conversion factors based on cosampled species and literature bioconcentration factors. The lowest metal and tributyltin concentrations were below background assessment concentrations (BACs) agreed in the Oslo-Paris convention (OSPAR) for the North Sea, and at most harbours the concentrations were orders of magnitude above BACs. The lowest concentrations of Cd and Pb measured here suggest that the BACs should be lower in a worldwide context. The sources of metals were classified according to human impact using principal component analysis. High relative concentrations of Hg, Pb and P were source indicators for industrial activity and land use; Zn, organotins, Cd and Cu for shipping activities, and V for oil spills. Generally the concentration levels at reference sites were low, but not always lower than expected impacted areas. The most contaminated areas were harbours, where especially Copenhagen, St Croix and Sydney, can be considered hotspots of tributyltin as well as a number of metals.

Polychlorinated biphenyls, organochlorine pesticides and polycyclic aromatic hydrocarbons in a one-off global survey of bivalves.

During the Danish Galathea 3 expedition, bivalve samples were collected at the Faroe Islands, Greenland, Ghana, South Africa, Australia, Solomon Islands, New Zealand, Chile, US Virgin Islands, Boston, Newfoundland and Shetland Islands and analysed for organochlorines and PAHs. Concentration differences of up to three orders of magnitude were observed, with the highest concentrations at Boston harbour (SPCB 338 ng g(-1) dw, ΣSPAH 5966 ng g(-1) dw) and the Sydney estuary (ΣSPCB 282 ng g(-1) dw, SPAH 1453 ng g(-1) dw). Local impacts were also found for the Greenland capital Nuuk in terms of PCB and PAH levels, while other Greenland samples came closest to representing PAH background levels. Several locations had undetectable organochlorine levels, including Hobart and Chile, which had the lowest SPAH concentrations (<200 ng g(-1) dw). It was possible to group the stations according to their pyrogenic/petrogenic influence using Principal Component Analyses, and indications of petroleum sources were found at Nuuk.

Dioxin concentrations in sediments of the Baltic Sea--a survey of existing data.

Recent survey results for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs, dioxins) in Baltic Sea sediments from Finland, Sweden and Denmark were merged with previously published Baltic Sea data. Regional distribution of concentration levels, differences in congener patterns, and temporal changes in sediment profiles were examined. One of the main objectives was to study if any major point sources for different PCDD/F congeners could be identified on a regional scale, based on sediment records. The survey confirmed the impact of chlorophenol production derived highly chlorinated PCDF-congeners on the total toxicity in sediments in the Gulf of Finland near the Kymijoki river estuary. Signatures of other point sources or combined point sources pertinent to specific industry branches or particular production processes (such as pulp bleaching, vinyl chloride production, thermal processes) may be discerned. However, the findings did not support any of the known point sources significantly influencing those congeners that are most abundant in Baltic herring and salmon. Instead, regional distributions in the Baltic Sea indicate that atmospheric deposition may act as a major source for those congeners and especially for 2,3,4,7,8-PeCDF. There were clear indications of declines in levels in sediment in some areas, but generally the levels of highly chlorinated PCDD/Fs on the northern coast of the Gulf of Finland were still high when compared with other areas of the Baltic Sea. Major areas with data gaps cover the south-eastern and eastern coastal regions of the Baltic Proper and the southern Gulf of Finland.

Accumulation of organotin compounds and mercury in harbour porpoises (Phocoena phocoena) from the Danish waters and West Greenland.

The concentrations of butyltin (summation operatorBT=TBT+DBT+MBT) and mercury (Hg) were determined in the liver of 35 harbour porpoises (Phocoena phocoena), which were found dead along the coastlines or caught as by-catch in the Danish North Sea and the Inner Danish waters. In addition, three harbour porpoises hunted in West Greenland were analysed. High levels of butyltin and mercury, within the range of 68-4605 mg BT/kg ww and 0.22-92 mg Hg/kg ww, were found in the liver of the Danish harbour porpoises and both substances tend to accumulate with age. The levels in the harbour porpoise from West Greenland were 2.0-18 mg BT/kg ww and 6.3-6.9 mg Hg/kg ww, respectively. The concentrations of butyltin and mercury were both found to be higher in stranded than in by-caught harbour porpoises but only the butyltin concentration was significantly higher in stranded porpoises in the age group 1-5 years. These substances are suspected of inducing adverse effects on immune and endocrine systems in mammals and they may thereby pose a threat to the animals. This study suggests that organotin compounds are also important, when assessing the risks of contaminants on the health and viability of harbour porpoises in Danish waters.

Biosensors for detection of mercury in contaminated soils.

Biosensors based on whole bacterial cells and on bacterial heavy metal binding protein were used to determine the mercury concentration in soil. The soil samples were collected in a vegetable garden accidentally contaminated with elemental mercury 25 years earlier. Bioavailable mercury was measured using different sensors: a protein-based biosensor, a whole bacterial cell based biosensor, and a plant sensor, i.e. morphological and biochemical responses in primary leaves and roots of bean seedlings grown in the mercury-contaminated soil. For comparison the total mercury concentration of the soil samples was determined by AAS. Whole bacterial cell and protein-based biosensors gave accurate responses proportional to the total amount of mercury in the soil samples. On the contrary, plant sensors were found to be less useful indicators of soil mercury contamination, as determined by plant biomass, mercury content of primary leaves and enzyme activities.