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Methylmercury (MeHg) is one of the most toxic compounds, it bioaccumulates and biomagnifies along the food chain and finally damages human's nervous system. Knowing that the main intake route for MeHg in humans is through fish consumption, intake rates were studied in various countries, but not in Belgium. Based on Hg and MeHg measurements in various fishes, mainly from North Sea catches, in combination with the national food consumption surveys, we could calculate daily Hg and MeHg intake rates for the Belgian population in 1975, 1997 and 2014-2021. These values are then compared with daily intake values reported by other countries and with the acceptable daily intake (ADI) values recommended by international organizations. Daily Hg and MeHg intake rates decreased strongly between 1975 and the 2 later periods: while average intake rates are all below the ADI norms, this is not the case for the 95th percentile rates because they exceed or are very close to the ADI values. Since daily MeHg intake rates correlate well with hair and blood concentrations, these were used as a good proxy of MeHg intoxication and were related to health effects observed in children, adolescents, adults and elderly persons living in Belgium via biomonitoring., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Contrary to the initial hypothesis, Flemish adolescents who reported consuming organic food at least 7.5 times per week did not exhibit reduced internal exposure to the tested recently used pesticides. After adjustment for gender, age, country of origin, socioeconomic status, body mass index, consumption of high-fat foods and foods linked to organic food consumption, and concerning organochlorine derivatives and lead, additional adjustment for the duration of breastfeeding expressed in weeks, they displayed slightly elevated internal exposure to organochlorine derivatives, lead, methyl arsenate, and toxic relevant arsenic. A comparison was also made between the correlation of internal exposure to pollutants with the frequency of organic food consumption on one hand and the total consumption of equivalent products from all sources on the other. Regarding potatoes, vegetables, and fruits, no clear trends were observed. Regarding eggs, there was a trend towards higher internal exposures with organic food consumption, significant for trans-nonachlor, PCB118, and 2,4-dichlorophenoxyacetic acid, and marginally significant for glyphosate. For dairy, there was a trend towards higher internal exposures with organic food consumption, significant for perfluorononanoic acid and marginally significant for PCB153. Regarding nuts and seeds, the higher internal exposure to dichlorophenoxyacetic acid and the lower exposure to 3-phenoxybenzoic acid were marginally significant, while there was also a trend towards higher internal exposure to other pollutants with organic food consumption, significant for PCB118, PCB153, and sum PCBs, and marginally significant for trans-nonachlor. Concerning breakfast cereals and muesli, no clear trends were observed.

Trace metals and metalloids are groups of chemical elements that naturally occur in low concentrations and cycle in the environment driven by natural processes and human activities. They have a persistent and bio-accumulative tendency in the environment, and certain trace metals and metalloids have become a public health concern. This study assesses the concentration of eleven trace metals and a metalloid in sediments and catfish muscle from five study sites in the Eastern Tanzanian River basin. Forty catfish tissues and fifteen sediment samples were collected and analyzed using ICP-MS. Concentrations of As, Cd, Co, Pb, and Zn did not exceed the United States Environmental Protection Agency (USEPA) guideline for pollution of sediments, while Al Cr, Al, Mn, and V with values ranging from (118.54 to 70154.55) indicating moderately polluted. The stations Java-Sadaani and Matandu showed the highest Cr, Ni, and Cu concentrations, but the potential ecological risk index (RI) was low (RI < 95). In the catfish muscle tissue, the levels of Cd, Pb, Cu, and Zn did not surpass the EU and FAO/WHO limits and results ranged from 2.22 to 35.22mg/kg. Low levels of accumulation of Cd, Pb, and As were found in this study compared to catfish muscles from other studies, whereas the concentrations of other trace metals and metalloids analyzed had comparable results. Biota/sediment accumulation factors (BSAF) were all < 1. The weekly metal intake (MWI) results ranged from 6.89E-04 to 2.43E+01 μg/know-1week-1, indicating a low risk as the value did not exceed the FAO/WHO established Permissible Tolerable Weekly Intake (PTWI). The non-carcinogenic health risk result THQ was 4.43E-02 and the carcinogenic health risks result HI was 4.42E-05 which indicated tolerable levels of risks as both the values of the Target Hazard Quotient (THQ) and the Hazard Index (HI) was < 1, and the carcinogenic target risk (TR) is < 0.0001. The highest TR values were observed for Cr and Ni. We recommend a continued monitoring of the changes in trace metal levels in the environment and biota together with continuous public health education on the dangers of high levels of trace metals., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Mayila et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

In this study, the vertical distribution of mercury (Hg) in estuarine and marine sediment porewaters and solid phases was assessed by conventional and passive sampling techniques in the historically polluted Scheldt Estuary and Belgian Coastal Zone (BCZ). The Diffusive Gradients in Thin-films (DGT) measured labile Hg concentrations (Hg LA ) were mostly lower than the porewater Hg concentrations (Hg PW ), and they also presented different vertical distribution patterns. Still high Hg concentrations in the sediment solid phases, comparable to the historical ones, were observed. Even though pH, redox potential and dissolved sulfide concentration could influence the Hg biogeochemical behaviour, organic matter (OM) played a key role in governing Hg mobilization from sediment solid phase to porewater and in its partitioning between porewater and solid phase over depth. In the marine sediments, where OM had a marine signature, higher labile Hg concentrations in the porewater and faster resupply from the solid phase were observed. The DGT technique showed significant potential not only for the measurement of bioavailable Hg fractions in porewater, but also for the assessment of kinetic parameters governing the release of labile Hg species from the solid phase with the assistance of the DGT Induced Fluxes in Sediments (DIFS) model., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Tianhui Ma reports financial support was provided by Research Foundation Flanders. Vincent Perrot reports financial support was provided by Research Foundation Flanders., (Copyright © 2023 Elsevier B.V. All rights reserved.)

It is well-known that the geochemical behavior of phosphorus (P) in sediments is closely related to that of Fe and Mn, but their relations remain unclear in long-term sulfidic sediments such as those of the Gotland Basin in the Baltic Sea. Therefore, P mobilization in these sediments at both shallow and deep sites was investigated in relation to that of Fe, Mn, and S. To achieve that aim, classic sediment slicing and subsequent solid phase sequential extraction were combined with in situ DGT (Diffusive Gradients in Thin-films) sampling, DIFS (DGT induced flux in sediments) modelling, and Visual MINTEQ calculations. Correlations between total dissolved and labile dissolved concentrations of P, Mn, and Fe in porewater, and the associations between labile fractions of these elements in the solid phase suggested two kinds of sources for P: The dissolution of P-bearing Fe oxides and/or Mn carbonates was observed in the shallower sites, while P and Mn release from different solid sources was observed in the deepest sites. Although the formation of Fe sulfides leads to extremely low dissolved Fe level in porewater, the simultaneous release of P with Mn/Fe was confirmed by theoretical calculations with Visual MINTEQ. The DIFS model showed that the resupply ability of P from sediment solids is determined by labile pool size. The application of experimental and theoretical methods made it possible to clarify the relationships between P, Fe, Mn and S in sulfidic sediments which may contribute to a better understanding of the P cycle in other sulfidic regions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Microplastics (MPs) are pervasive in marine environments and widely recognized as emerging environmental pollutants due to the multifaceted risks they exert on living organisms and ecosystems. Sponges (Phylum Porifera) are essential suspension-feeding organisms that may be highly susceptible to MPs uptake due to their global distribution, unique feeding behavior, and sedentary lifestyle. However, the role of sponges in MP research remains largely underexplored. In the present study, we investigate the presence and abundance of MPs (≤10 μm size) in four sponge species, namely Chondrosia reniformis, Ircinia variabilis, Petrosia ficiformis, and Sarcotragus spinosulus collected from four sites along the Mediterranean coast of Morocco, as well as their spatial distribution. MPs analysis was conducted using an innovative Italian patented extraction methodology coupled with SEM-EDX detection. Our findings reveal the presence of MPs in all collected sponge specimens, indicating a pollution rate of 100%. The abundance of MPs in the four sponge species ranged from 3.95×10 5 to 1.05×10 6 particles per gram dry weight of sponge tissue, with significant differences observed among sampling sites but no species-specific differences. These results imply that the uptake of MPs by sponges is likely influenced by aquatic environmental pollution rather than the sponge species themselves. The smallest and largest MPs were identified in C. reniformis and P. ficiformis, with median diameters of 1.84 μm and 2.57 μm, respectively. Overall, this study provides the first evidence and an important baseline for the ingestion of small MP particles in Mediterranean sponges, introducing the hypothesis that they may serve as valuable bioindicators of MP pollution in the near future., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interestsMargherita, Ferrante and Gea Oliveri Conti, have patent #International Application No. PCT/IB 2019/051,838 Italian patent n. 102018000003337–07 March 2018, European patent n.3788344 July 20, 2022 licensed to Italian Minister and EU patent office. No other conflict of interest is disclosed., (Copyright © 2023 Elsevier Inc. All rights reserved.)

The colloidal transport of trace (Fe, Al, Ba, Pb, Sr, U) and ultra-trace ( 226 Ra) elements was studied in a mining environment. An original approach combining 0.45 μm filtered water sampling, the Diffusive Gradient in Thin films (DGT) technique, mineralogical characterization, and geochemical modelling was developed and tested at 17 sampling points. DGT was used for the truly dissolved fraction of the elements of interest, while the 0.45 μm filtration includes both colloidal and truly dissolved fractions (together referred to as total dissolved fraction). Results indicated a colloidal fraction for Al (up to 50%), Ba (up to 86%), and Fe (up to 99%) explained by the presence of submicrometric grains of kaolinite, barite, and ferrihydrite, respectively. Furthermore, the total dissolved 226 Ra concentration in the water samples reached up to 10-25 Bq/L (1.2-3.0 10 -12  mol/L) at 3 sampling points, while the truly dissolved aqueous 226 Ra concentrations were in the mBq/L range. Such high total dissolved concentrations are explained by retention on colloidal barite, accounting for 95% of the total dissolved 226 Ra concentration. The distribution of 226 Ra between the truly dissolved and colloidal fractions was accurately reproduced using a (Ra x ,Ba 1-x )SO 4 solid solution, with values of the Guggenheim parameter a 0 close to ideality. 226 Ra sorption on ferrihydrite and kaolinite, other minerals well known for their retention properties, could not explain the measured colloidal fractions despite their predominance. This illustrates the key role of barite in such environments. The measured concentrations of total dissolved U were very low at all the sampling points (<4.5 10 -10  mol/L) and the colloidal fraction of U accounted for less than 65%. U sorption on ferrihydrite could account for the colloidal fraction. This original approach can be applied to other trace and ultra-trace elements to complement when necessary classical environmental surveys usually performed by filtration on 0.45 μm., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The geochemical behavior of metals in water and sediment was investigated in the tidal section of the Zenne River in Belgium. Twelve-hour sampling campaigns were performed in October 2013 and March 2021 at the mouth of the Zenne River, under dry and rainy weather conditions respectively. Water samples were collected every hour while the passive samplers of Diffusive Gradients in Thin-films (DGT) were deployed continuously during a tidal cycle. In addition, bottom sediments were sampled at the tidal station and water samples were taken upstream and downstream of that station to identify the metal sources. The highest concentrations of Fe, Mn, Pb, Cr, Ni and Zn appear at low tide, indicating the Zenner River as a main source. However, for Co, Cd and Cu, other sources including upstream transport may explain their behavior during a tidal cycle. Fe, Pb and Cr are essentially transported in the particulate phase (<10 % dissolved) while the other metals in the dissolved phase (20 to 90 %). Rainfall and wind gust events also play an important role in trace metal distribution, increasing sediment resuspension and metal desorption. A good agreement was found between the time-averaged dissolved and DGT-labile metal concentrations with the exception of Cu and Fe, which form strong organic Cu complexes and Fe colloids respectively. The sediments of the tidal Zenne are contaminated by trace metals, thus acting as a secondary pollution source to the river. The reductive dissolution of Mn and Fe oxyhydroxides and the release of associated trace metals are the main mobilization mechanisms. Knowledge of the upstream and downstream levels in the water column, the benthic fluxes, which are based on turbulent diffusion, and the partitioning between dissolved and particulate phases allow to explain the metal concentration variations during the tidal cycle., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Estuaries and coastal zones are areas with complex biogeochemical and hydrological cycles and are generally facing intense pollution due to anthropogenic activities. An emblematic example is the Scheldt Estuary which ends up in the North Sea and has been historically heavily contaminated by multiple pollutants, including mercury (Hg). We report here Hg species and their levels in surface waters of the Scheldt Estuary and the Belgian Part of North Sea (BPNS) from different sampling campaigns in February-April 2020 and 2021. Along the estuary, Hg concentration on suspended particles ([Hg SPM ]) progressively decreased with increasing salinity and was strongly correlated with organic matter content (%C org ) and origin (identified with δ 13 C org ). While [Hg SPM ] drives total Hg concentration in the estuary (total dissolved Hg, Hg TD is only 7 ± 6 %), annual and daily variations of total Hg levels were mostly attributed to changes in SPM loads depending on river discharge and tidal regime. In the BPNS, a significant fraction of total Hg occurs as Hg TD (40 ± 21 %) and the majority of this Hg TD was reducible (i.e. labile Hg), meaning potentially available for microorganisms. Compared to the '90s, a significant decrease of [Hg SPM ] was observed in the estuary, but this was not the case for [Hg TD ], which can be due to (1) still significant discrete discharges from Antwerp industrial area, and (2) higher Hg partitioning towards the dissolved phase in the water column relative to the '90s. Our results highlight the important contribution of the Scheldt estuary for the Hg budget in North Sea coastal waters, as well as the need for seasonal monitoring of all Hg species., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The distribution and geochemistry of arsenic (As) in water and sediments of the Zenne River, a small urban river flowing through Brussels (Belgium), were assessed based on the results of 18 sampling campaigns performed between 2010 and 2021. In general, concentrations of As sharply increase between Vilvoorde and Eppegem and are up to 6-8 times higher in the section downstream of Eppegem in comparison to the upstream part of the Zenne. The monitoring surveys in which the grab water samples were taken at a 1-hour sampling frequency revealed that the large temporal variability in As concentrations found in the downstream part of the river is driven by the tidal cycle. The diffusive gradients in thin films (DGT) technique was used to assess the DGT labile As species in surface water and sediment porewater. Three DGT sorbents (Metsorb, Lewatit FO 36, and ZrO 2 ) for the determination of total As were applied to compare their performance, and the 3-mercaptopropyl-functionalized silica (3-MFS) was used for the speciation of As(III) in porewater. Arsenic species are fully labile in surface waters as the DGT time-integrated concentrations of As were in good agreement with the average concentrations calculated from the grab samplings. In sediment porewaters, As is predominantly present as non-DGT labile species (66-93 %), and the DGT labile As fraction is dominated by As(III). Flux calculations evaluating the relative importance of different As sources to the Zenne River revealed the presence of a point source on the tributary Tangebeek, which contributes to 87 % of the As load carried by the Zenne River., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Eutrophication and global change are increasing the occurrence of seasonal hypoxia (bottom-water oxygen concentration <63 μM) in coastal systems worldwide. In extreme cases, the bottom water can become completely anoxic, allowing sulfide to escape from the sediments and leading to the development of bottom-water euxinia. In seasonally hypoxic coastal basins, electrogenic sulfur oxidation by long, filamentous cable bacteria has been shown to stimulate the formation of an iron oxide layer near the sediment-water interface, while the bottom waters are oxygenated. Upon the development of bottom-water anoxia, this iron oxide "firewall" prevents the sedimentary release of sulfide. Iron oxides also act as an adsorption trap for elements such as arsenic. Arsenic is a toxic trace metal, and its release from sediments can have a negative impact on marine ecosystems. Yet, it is currently unknown how electrogenic sulfur oxidation impacts arsenic cycling in seasonally hypoxic basins. In this study, we presented results from a seasonal field study of an uncontaminated marine lake, complemented with a long-term sediment core incubation experiment, which reveals that cable bacteria have a strong impact on the arsenic cycle in a seasonally hypoxic system. Electrogenic sulfur oxidation significantly modulates the arsenic fluxes over a seasonal time scale by enriching arsenic in the iron oxide layer near the sediment-water interface in the oxic period and pulse-releasing arsenic during the anoxic period. Fluxes as large as 20 μmol m -2 day -1 were measured, which are comparable to As fluxes reported from highly contaminated sediments. Since cable bacteria are recognized as active components of the microbial community in seasonally hypoxic systems worldwide, this seasonal amplification of arsenic fluxes is likely a widespread phenomenon., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 van de Velde, Burdorf, Hidalgo-Martinez, Leermakers and Meysman.)

The present research aimed to investigate the concentrations and patterns of six potentially toxic elements (PTEs) in three common sponge species collected along the Moroccan Mediterranean coast, as well as their levels in ambient seawater and sediments. Distinct inter-species variability in PTEs bioaccumulation was observed among the three species, suggesting that sponges have distinct selectivity for assimilating PTEs from the surrounding environment. C. crambe had a higher enrichment capacity for Cu, As, Cr and Ni, while P. ficiformis and C. reniformis exhibited the highest concentration of Cd and Pb, respectively. Interestingly, a similar spatial distribution patterns of PTEs was observed in the three media, with high values occurring in Tangier and Al-Hoceima locations. Overall, our results confirm that sponges reliably reflect the bioavailability of PTEs in their immediate environment, especially C. crambe, whose PTE tissue contents were highly and positively correlated with the contents of all PTEs in the sediments., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Monitoring of uranium in the environment using the Diffusive Gradients in Thin-films (DGT) technique gains in importance as it can provide unique information about the bioavailability of the element and allows its long-term in-situ measurement. Hence, in this study, four DGT binding phases (Chelex-100, Dow-PIWBA, Diphonix, and Lewatit FO 36 resins) were evaluated for uranium monitoring to assess the robustness of their performance in estuarine and marine environments. These DGTs were deployed along the Scheldt estuary (Belgium and the Netherlands) over four campaigns between 2014 and 2021. The DGT performance (ratio of the DGT-determined vs. dissolved U concentration in grab water sample) varied with the water salinity. The Chelex-100 DGTs generally provided good performance in freshwater (median ratios close to 1.0), but an inverse correlation with the increasing salinity was observed (median ratios 0.7 at the stations with salinity >5). The Lewatit FO 36 DGTs provided good performance in the salinity range 0-18 (median ratios 1.0). However, a strong negative influence was observed at stations with high salinity levels (>18, ratio 0.6) and during the long-term deployment in seawater (ratios <0.5 over deployment periods ≥2 days). The Dow-PIWBA and Diphonix DGTs provided overall similar results with excellent performances along the whole salinity gradient (median ratios 1.1 and 1.0, respectively). Nevertheless, the long-term deployment trial in seawater (salinity ∼27) revealed the robustness of Diphonix DGTs that provided outstanding results even after 28 days of deployment (ratio 1.0). The differences in the performance of tested DGT resins were mostly given by the changes of U speciation along the salinity gradient. The speciation modelling of U showed that calcium uranyl carbonate complexes dominate along the Scheldt estuary (from 97 to 86% seawards) with increasing fraction of UO 2 (CO 3 ) 3 4- (from 2 to 14%) towards the mouth., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The population of the semi-arid areas of the countries in the East African Rift Valley (EARV) is faced with serious problems associated with the availability and the quality of the drinking water. In these areas, the drinking water supply largely relies on groundwater characterised by elevated fluoride concentration (> 1.5 mg/L), resulting from interactions with the surrounding alkaline volcanic rocks. This geochemical anomaly is often associated with the presence of other naturally occurring potentially toxic elements (PTEs), such as As, Mo, U, V, which are known to cause adverse effects on human health. This study reports on the occurrence of such PTEs in the groundwater on the populated flanks of Mt. Meru, an active volcano situated in the EARV. Our results show that the majority of analysed PTEs (Al, As, Ba, Cd, Cr, Cu, Fe, Mn, Ni, Se, Sr, Pb, and Zn) are within the acceptable limits for drinking purpose in samples collected from wells, springs and tap systems, suggesting that there is no immediate health risk associated with these PTEs. However, some of the samples were found to exceed the WHO tolerance limit for U (> 30 μg/L) and Mo (> 70 μg/L). The sample analysis also revealed that in some of the collected samples, the concentrations of total dissolved solids, Na +  and K +  exceed the permissible limits. The concerning levels of major parameters and PTEs were found to be associated with areas covered with debris avalanche deposits on the northeast flank, and volcanic ash and alluvial deposits on the southwest flanks of the volcano. The study highlights the need to extend the range of elements monitored in the regional groundwater and make a more routine measurement of PTEs to ensure drinking water safety and effective water management measures., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

To improve our understanding of internal exposure to multiple chemicals, the concept exposure load (EL) was used on human biomonitoring (HBM) data of the 4th FLEHS (Flemish Environment and Health Study; 2016-2020). The investigated chemicals were per- and polyfluoroalkyl substances (PFASs), bisphenols, phthalates and alternative plasticizers, flame retardants, pesticides, toxic metals, organochlorine compounds and polycyclic aromatic hydrocarbons (PAHs). The EL calculates "the number of chemicals to which individuals are internally exposed above a predefined threshold". In this study, the 50th and 90th percentile of each of the 45 chemicals were applied as thresholds for the EL calculations for 387 study participants. Around 20% of the participants were exposed to >27 chemicals above the P50 and to >6 chemicals above the P90 level. This shows that participants can be internally exposed to multiple chemicals in relatively high concentrations. When the chemical composition of the EL was considered, the variability between individuals was driven by some chemicals more than others. The variability of the chemical profiles at high exposure loads (EL-P90) was somewhat dominated by e.g. organochlorine chemicals, PFASs, phthalates, PAHs, organophosphate flame retardants, bisphenols (A & F), pesticides, metals, but to a lesser extent by brominated flame retardants, the organophosphorus flame retardants TCIPP & TBOEP, naphthalene and benzene, bisphenols S, B & Z, the pesticide 2,4-D, the phthalate DEP and alternative plasticizer DINCH. Associations between the EL and exposure determinants suggested determinants formerly associated with fat soluble chemicals, PFASs, bisphenols, and PAHs. This information adds to the knowledge needed to reduce the exposure by policymakers and citizens. However, a more in depth study is necessary to explore in detail the causes for the higher EL in some individuals. Some limitations in the EL concept are that a binary number is used for exposure above or below a threshold, while toxicity and residence time in the body are not accounted for and the sequence of exposure in different life stages is unknown. However, EL is a first useful step to get more insight in multiple chemical exposure in higher exposed subpopulations (relative to the rest of the sampled population)., (Copyright © 2021. Published by Elsevier GmbH.)

Freshly erupted volcanic ash contains a range of soluble elements, some of which can generate harmful effects in living cells and are considered potentially toxic elements (PTEs). This work investigates the leaching dynamics of ash-associated PTEs in order to optimize a method for volcanic ash respiratory hazard assessment. Using three pristine (unaffected by precipitation) ash samples, we quantify the release of PTEs (Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, V, Zn) and major cations typical of ash leachates (Mg, Na, Ca, K) in multiple simulated lung fluid (SLF) preparations and under varying experimental parameters (contact time and solid to liquid ratio). Data are compared to a standard water leach (WL) to ascertain whether the WL can be used as a simple proxy for SLF leaching. The main findings are: PTE concentrations reach steady-state dissolution by 24 h, and a relatively short contact time (10 min) approximates maximum dissolution; PTE dissolution is comparatively stable at low solid to liquid ratios (1:100 to 1:1000); inclusion of commonly used macromolecules has element-specific effects, and addition of a lung surfactant has little impact on extraction efficiency. These observations indicate that a WL can be used to approximate lung bioaccessible PTEs in an eruption response situation. This is a useful step towards standardizing in vitro methods to determine the soluble-element hazard from inhaled ash., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The performance of the newly developed DGT technique for the platinum group elements (PGEs) rhodium (Rh), platinum (Pt) and palladium (Pd) was evaluated in two tributaries of the Scheldt River, the Marque River close to the city of Lille (France), and the Zenne River which flows through the city of Brussels (Belgium). In the Marque River, an interlaboratory comparison was performed between the two laboratories where the DGT techniques dedicated to PGEs were developed (AMGC, VUB & LASIRE, U-Lille). PGEs were also analysed in an effluent of a Brussels hospital and monthly grab sampling was performed at the wastewater treatments plants (WWTPs) of Brussels. The concentrations of the 3 elements are higher in the Zenne River than in the Marque River and much higher Pt concentrations are found in the hospital effluent. Good agreement for Pt was observed between the three selected chelating resins and a relatively good agreement was observed between the two laboratories using the same chelating resin, whereas lower results were observed with the anion-exchange resin. Larger discrepancies between the two laboratories were observed for Pd and no comparison could be made for Rh due to the low natural concentrations. The results show that in small urban rivers with high impact of urbanization, WWTPs are an important source of Pt, resulting from the use of anticancer drugs in hospitals and households. The limited retention of PGEs in WWTPs results in increased concentrations in urban rivers downstream. For Pd and Rh, similar trends were found with other traffic related elements such as Cu, Zn and Pb, showing the highest concentrations in waters collecting runoff from a highway. The data show that these elements, together with Gd, can be useful to trace specific pollution sources and their dispersion., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The sorption ability of Lewatit FO 36-DGT resin gel, which has been developed for arsenic determination, towards uranium was tested by batch experiments within this study for the first time. Since the uptake efficiency of uranium was 99.0 ± 0.4% and the maximum uptake capacity was not achieved even at the U spike of 1250 μg in the solution, the Lewatit FO 36 resin seems to be a suitable binding phase for DGT resin gels for the determination of uranium. The resin gel also does not display any significant sorption selectivity in favour of one element over another. A novel protocol for simultaneous elution of arsenic and uranium from Lewatit FO 36 resin gel was therefore proposed in this study. The elution efficiencies of 90.3 ± 3.9% and 85.2 ± 3.1% for As and U, respectively, were obtained using 5 mL of 1 M NaOH at 70 °C for 24 h. The comparison with the original elution protocol using microwave-assisted elution by 0.25 M NaOH and 0.17 M NaCl at 130 °C for 16 min indicates, that the novel elution protocol provides good results in the performance of arsenic elution and, in addition, allows simultaneous elution of uranium. Moreover, the elimination of NaCl from the elution process allows a fast and simple analysis of both elements using ICP-MS, and therefore, the Lewatit FO 36-DGT technique can become more commonplace among laboratories without the need to modify the analytical method as proposed in the original study., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The speciation of trace metals in an aquatic system involves the determination of free ions, complexes (labile and non-labile), colloids, and the total dissolved concentration. In this paper, we review the integrated assessment of free ions and labile metal complexes using Diffusive Gradients in Thin-films (DGT), a dynamic speciation technique. The device consists of a diffusive hydrogel layer made of polyacrylamide, backed by a layer of resin (usually Chelex-100) for all trace metals except for Hg. The best results for Hg speciation are obtained with agarose as hydrogel and a thiol-based resin. The diffusive domain controls the diffusion flux of the metal ions and complexes to the resin, which strongly binds all free ions. By using DGT devices with different thicknesses of the diffusive or resin gels and exploiting expressions derived from kinetic models, one can determine the labile concentrations, mobilities, and labilities of different species of an element in an aquatic system. This procedure has been applied to the determination of the organic pool of trace metals in freshwaters or to the characterization of organic and inorganic complexes in sea waters. The concentrations that are obtained represent time-weighted averages (TWA) over the deployment period., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Galceran, Gao, Puy, Leermakers, Rey-Castro, Zhou and Baeyens.)

The analysis of platinum (Pt), palladium (Pd) and rhodium (Rh) in aquatic samples by the diffusive gradients in thin films (DGT) technique using chelating resins, specific designed for the accumulation of PGEs, namely Purolite S914, S920 and Italmatch Chemicals IONQUEST® MPX-317. may however, still be influenced by the accumulation of other elements such (Cu, Zn, Pb, etc.) which will be extracted simultaneously by the hot aqua regia extraction and interfere with the Inductively Coupled Plasma Mass Spectrometry (ICPMS) analysis of the Platinum Group Elements (PGEs). Selective extractions were investigated to release the interfering elements without loss of the Platinum Group Elements (PGEs) from the resin gels. . A rinse with deionized water removes over 95% of Sr and Rb and a second rinse with 0.05 mol L -1  H 2 SO 4 can be used to as a common eluent to remove an important fraction of the interfering elements from S920 and S914 without loss of PGEs but this results in loss of around 15% of the PGEs from MPX-317. It was shown that selective extractions can be used to remove specific interferences from each resin gel., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Diffusive gradients in thin-films (DGT) is an in situ passive sampling technique to assess labile trace metal concentrations in different environmental matrix. The technique is consisting of a diffusive domain backed up by a resin gel that binds free metals and metal complexes that dissociate in the diffusive domain. This technique requires specific resin for special metals, for example mercury (Hg), since the classic resin (Chelex-100) gel is not applicable for Hg measurement. A simultaneous determination of Hg with other metals by the DGT was not yet reported. Two biomolecule-based resins were prepared by glutaraldehyde immobilisation of cysteine onto 3-amino-functionalised silica and 3-aminopropyl-functionalised silica, respectively. The load of functional groups on modified resins was qualitatively and quantitatively characterised. The modified resins were applied in the DGT technique and the uptake efficiency, elution efficiency, and linear accumulation of analytes of the DGT were tested. This novel DGT technique, using two cysteine-modified resins, can accumulate Hg and other metals in a broad range of pH and ionic strength in solutions. In the Belgian coastal zone (BCZ), the concentrations of Hg and other trace metals sampled by cysteine-modified resin-DGTs were similar as those by the other two DGT assemblies for Hg and other trace metals, respectively. The cysteine-modified silica resin combined the features of Chelex-100 resin and 3-mercaptopropyl silica resin and allowed simultaneous determination of labile Hg and other trace metals. The resin with a higher load of functional groups also showed higher performance in the further application in the DGT technique., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The analysis of mercury in food presents a challenge for analytical chemists. Sample pre-treatment and the preconcentration of mercury prior to measurement are required, even when highly sensitive analytical methods are used. In this work, the Diffusive Gradients in Thin Films technique (DGT), combined with thermal decomposition gold amalgamation atomic absorption spectrometry (TDA-AAS), was investigated for the determination of the total dissolved mercury in fish sauces. Moreover, a new type of binding gel with Purolite S924 resin was used in DGT. Linearity assays for DGT provided determination coefficients around 0.995. Repeatability tests showed a relative standard deviation of less than 10%. pH values in the range of 3-6, as well as NaCl concentrations up to 50 g·L -1 , did not affect the performance of DGT. The effective diffusion coefficient of mercury in five-fold diluted fish sauce was determined to be (3.42 ± 0.23)·10 -6 cm 2 ·s -1 . Based on the 24 h deployment time of DGT, the limit of detection (LOD) for the investigated method was 0.071 µg·L -1 . The proposed method, which combines DGT and TDA-AAS, allows for the analysis of fish sauces with mercury concentrations below the LOD of TDA-AAS, and significantly reduces the wear and corrosion of the TDA-AAS components.

Digestate treatment techniques have recently been proposed as a strategy to increase the ultimate biogas yield from dairy manure and to improve the digestate quality as an organic fertilizer. These studies however rarely take the trace elements (TE) and nutrient partitioning into account. This study focusses on ozone treatment (5-40 g O 3 kg -1 Total Solids (TS)) as a digestate treatment technique to control the concentration of TE and nutrients in the liquid phase of the digestate. Controlling the TE and nutrient concentrations in the liquid and solid digestate can improve the agronomic value of dairy manure digestate. The ozone concentration of the gas stream entering reactor was 48.53 g O 3 /Nm³ or 3.4% w/w O 3 in O 2 -gas. The experiments were repeated using pure oxygen gas to investigate its influence. The results from ozonation and oxygenation of the dairy manure digestates revealed that O 3 treatment up to 40 g O 3 kg -1 TS did not have a more pronounced effect on the biochemical parameters compared to supplementation of pure O 2 . Ozonation of the digestate and the supernatant showed that the TE concentration in the liquid phase followed a parabolic profile. The observed initial increase in this parabolic profile was explained by the release of TE from the organic matter to the supernatant causing an increase in TE concentration, followed by a decrease due to precipitation of TE as hydroxides and sulfides, due to the increasing pH and sulphur concentrations., Competing Interests: Declaration of competing interest None., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Corynebacterium diphtheriae is a human pathogen that causes diphtheria. In response to immune system-induced oxidative stress, C. diphtheriae expresses antioxidant enzymes, among which are methionine sulfoxide reductase (Msr) enzymes, which are critical for bacterial survival in the face of oxidative stress. Although some aspects of the catalytic mechanism of the Msr enzymes have been reported, several details still await full elucidation. Here, we solved the solution structure of C. diphtheriae MsrB (Cd-MsrB) and unraveled its catalytic and oxidation-protection mechanisms. Cd-MsrB catalyzes methionine sulfoxide reduction involving three redox-active cysteines. Using NMR heteronuclear single-quantum coherence spectra, kinetics, biochemical assays, and MS analyses, we show that the conserved nucleophilic residue Cys-122 is S -sulfenylated after substrate reduction, which is then resolved by a conserved cysteine, Cys-66, or by the nonconserved residue Cys-127. We noted that the overall structural changes during the disulfide cascade expose the Cys-122-Cys-66 disulfide to recycling through thioredoxin. In the presence of hydrogen peroxide, Cd-MsrB formed reversible intra- and intermolecular disulfides without losing its Cys-coordinated Zn 2+ , and only the nonconserved Cys-127 reacted with the low-molecular-weight (LMW) thiol mycothiol, protecting it from overoxidation. In summary, our structure-function analyses reveal critical details of the Cd-MsrB catalytic mechanism, including a major structural rearrangement that primes the Cys-122-Cys-66 disulfide for thioredoxin reduction and a reversible protection against excessive oxidation of the catalytic cysteines in Cd-MsrB through intra- and intermolecular disulfide formation and S -mycothiolation., (© 2020 Tossounian et al.)

Knowledge on the bioavailability of trace elements is essential in developing environmental quality standards. The purpose of this study was to explore the relationships between trace elements (in particular Uranium (U)) in sediments, porewater and their bioaccumulation by Chironomus riparius on a uranium mining site and river sediments upstream of the mine. The mobility and speciation of U in sediments was investigated using DGT. Geochemical modelling using CHESS provided insight on sorption behavior of U on ironoxyhydrite (HFO) and aqueous speciation of U. In the upstream site U concentrations found were 0.05 μmol g -1 in surface sediment, 0.84 nmol L -1 in porewater and 2.4 nmol g -1 in Chironomus riparius whereas in the ferrihydrite deposits on the mining sites the concentrations found were up to 9.4 μmol g -1 in surface sediment, 0.37 μmol L -1 in porewater and 0.684 μmol g -1 in in Chironomus riparius. Despite the large differences in concentrations of U between the two sites, sediment to dissolved partitioning coefficients, bioconcentration factor (BCF) and biota sediment accumulation factors (BSAF) were very comparable. In the upstream sediment binding of U to organic matter controls sorption and aqueous speciation of U, whereas in the HFO rich sediments, sorption on HFO and the formation of HFO colloids are the determining factors. The low BSAF factors and high BCF factors indicate that the bioaccumulation is due to uptake from the dissolved phase. The DGT probes with different binding resins provide information on the colloidal nature and lability of the dissolved U species., (Copyright © 2019. Published by Elsevier Ltd.)

The Diffusive Gradients in Thin Films (DGT) technique was developed for the first time for the platinum group elements (PGEs) platinum (Pt), palladium (Pd), and rhodium (Rh). Different chelating resins, specific designed for the accumulation of PGEs, namely Purolite S914, S920, S985, Italmatch Chemicals IONQUEST ® MPX-317 and MP-102, were compared. The method development involved several different steps: 1) selection of an appropriate diffusive gel, 2) comparison of resins for the PGEs in terms of kinetics of uptake, 3) development of an efficient elution method for the PGEs from the resin gel, 4) Determination of diffusion coefficients for the PGEs in the diffusive gel, 5) Investigation of the influence of pH, ionic strength and dissolved organic matter on the diffusion coefficients and 6) study the selectivity of the tested resins gels in terms of potential interferences on the determination by ICPMS. Pt, Pd and Rh showed a linear accumulation over time for all resins and diffusion coefficients were independent of pH. The diffusion coefficient for Pt increased with increasing ionic strength (>0.5 M NaCl), but not for Pd and Rh. The interference study showed that Sr was the most important interferent for Rh and Pd and must be removed prior to analysis. The resins Purolite S914, Purolite S920, and Italmatch Chemicals IONQUEST ® MPX-317 showed the best performance in terms of detection limits and separation of interferences. Using optimized procedures, the concentrations of Pt, Pd and Rh can be quantified at pg L -1 levels in natural waters for a 14 day deployment time., (Copyright © 2019. Published by Elsevier B.V.)

Sequential extraction schemes (SES) were evaluated to investigate the fractionation of Al, As, Cd, Cs, Cr, Co, Cu, Fe, Mn, Mo, Pb, Sr, U and Zn between the different mineral phases in iron oxide rich deposits of a former uranium mining site. Ineffective dissolution of iron oxide was observed when applying the BCR sequential extraction scheme. The hydroxylamine hydrochloride reagent in nitric acid could not effectively dissolve the iron oxide phase, even after several consecutive extractions. The use of sodium pyrophosphate to remove organic matter prior to the dissolution of the iron oxides and the use of oxalic acid buffer and dithionite citrate buffer to dissolve the amorphous and crystalline iron oxides was evaluated. An alternative six step SES for iron oxide rich sediments is proposed consisting of F1) Exchangeable-Carbonate fraction using acetic acid/ sodium acetate buffer (pH 5) F2) Labile organic fraction using sodium pyrophosphate, F3) Easily reducible amorphous oxides using an oxalic acid buffer, F4) Organic and Sulfide fraction using hydrogen peroxide, followed by ammonium acetate extraction, F5) Poorly reducible crystalline oxides using sodium dithionite and F6) residual fraction using a microwave digestion step with hydrofluoric acid, nitric acid and hydrochloride acid mixture. A good correspondence between the sum of the sequential extraction steps and total metal concentrations was found. Both the BCR method and new method were also applied to the CRM BCR 701 providing indicative values for non-certified elements with the BCR method and indicative values for the method presented., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Sediment capping with activated carbon (AC) is an effective technique used in remediation of contaminated sediments, but the ecological effects on benthic microbial activity and meiofauna communities have been largely neglected. This study presents results from a 4-week experiment investigating the influence of two powdered AC materials (bituminous coal-based and coconut shell-derived) and one control material (clay) on biogeochemical processes and meiofauna in contaminated sediments. Capping with AC induced a 62-63% decrease in denitrification and a 66-87% decrease in dissimilatory nitrate reduction to ammonium (DNRA). Sediment porewater pH increased from 7.1 to 9.0 and 9.7 after addition of bituminous AC and biomass-derived AC, respectively. High pH (>8) persisted for at least two weeks in the bituminous AC and for at least 24 days in the coconut based AC, while capping with clay had no effect on pH. We observed a strong impact (nitrate fluxes being halved in presence of AC) on nitrification activity as nitrifiers are sensitive to high pH. This partly explains the significant decrease in nitrate reduction rates since denitrification was almost entirely coupled to nitrification. Total benthic metabolism estimated by sediment oxygen uptake was reduced by 30 and 43% in presence of bituminous coal-based AC and coconut shell-derived AC, respectively. Meiofauna abundances decreased by 60-62% in the AC treatments. Taken together, these observations suggest that AC amendments deplete natural organic carbon, intended as food, to heterotrophic benthic communities. Phosphate efflux was 91% lower in presence of bituminous AC compared to untreated sediment probably due to its content of aluminum (Al) oxides, which have high affinity for phosphate. This study demonstrates that capping with powdered AC produces significant effects on benthic biogeochemical fluxes, microbial processes and meiofauna abundances, which are likely due to an increase in porewater pH and to the sequestration of natural, sedimentary organic matter by AC particles., (Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Concentrations of Al, As, Bi, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, U, V and Zn were quantified in surface sediments collected from 13 different sampling sites from Cau Hai lagoon in Central Vietnam, and in 8 wild and farmed-fishes involving both pelagic and benthic species. Multivariate analysis shows that these trace elements are mainly associated with lithogenic matter, and are most likely the result of alteration and erosion processes in the lagoon. Enrichment factors and geo-accumulation indices reveal substantial sediment enrichments for both As and Bi with respect to the mean composition in the upper continental crust. As is enriched in the edible portion of fish tissue with values up to 10 times higher than the allowed limits set up by Health Canada. Target hazard quotient and target carcinogenic risk for As were assessed through fish diet and were greater than 1 and 10 -4 , respectively, indicating potential health risks for fish consumers in Cau Hai lagoon., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

In this first in situ study of the dynamic availability of phytoplankton micronutrients, a SeaExplorer glider was combined with Diffusive Gradients in Thin Films and deployed in the Mediterranean Sea. On the basis of their labile metal complex pools, we discovered that Fe and Co can be potentially limiting and Cu co-limiting to diatom growth, contrary to the generally accepted view that phosphorus (phosphate) is the growth limiting element in the Mediterranean Sea. For flagellates and picoplankton, phosphorus remains the main element limiting growth. Our in situ measurements showed that organic complexes of Fe and Cu (>98% of total dissolved concentration), dissociate slower than inorganic complexes of Co, Cd and Ni (>99% of total dissolved concentration being free ions and inorganic complexes). This strengthens the potential growth limiting effect of Fe and Cu versus phosphate, which is present as a free ion and, thus, directly available for plankton.

In North Sea and Port Açu (Brazil) coastal areas, high arsenic (As) concentrations were observed in water, soil and sediments. Therefore, the impact of this contamination on fish and shellfish species bought from local fishermen was studied. Total As was assessed with ICP-OES (Brazil) and ICP-MS (North Sea) after microwave digestion. Toxic As was assessed with liquid chromatography-ICP-MS (Brazil) and hydride generation-atomic fluorescence spectrometry (North Sea). All analytical methods comply with Quality Assurance/Quality Control procedures. Several fish species have average Total As concentrations above 1 μg g-1 wet weight (ww), but the highest concentrations are found in less spotted dogfish, lemon sole and whelks from the North Sea, with respectively 50, 49 and 50 μg g-1 ww. High Total As concentrations correspond to high Toxic As concentrations, except for scallops having increased Toxic As concentrations. Toxic As fractions are highest in scallops (almost 10%) but rarely exceeds 2% in all other species. Liver samples were only analyzed in ray, dogfish and catfish and their Toxic As fractions are between 2 and 4 times higher than in muscle. For a consumption of 150 g of seafood, only 3 samples exceed the provisional total daily intake of 2 μg kg-1 bw, however, cancer risks are non-negligible. Using mean Toxic As concentrations for each of the different fish and shellfish species studied, Lifetime Cancer Risk values at the actual global seafood consumption rate of 54 g day-1 are above 10-4 for whelks, scallops, dogfish, ray and lemon sole., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The coastal population in East Africa is growing rapidly but sewage treatment and recycling facilities in major cities and towns are poorly developed. Since estuarine mangroves are the main hotspots for pollutants, there is a potential for contaminants to accumulate in edible fauna and threaten public health. This study analysed trace metals in muscle tissues of the giant mud crabs (Scylla serrata) and the giant tiger prawns (Penaeus monodon) from the Tanzanian coast, in order to determine the extent of bioaccumulation and public health risks. A total of 180 samples of muscle tissues of S. serrata and 80 of P. monodon were collected from nine sites along the coast. Both species showed high levels of trace metals in the wet season and significant bioaccumulation of As, Cu and Zn. Due to their burrowing and feeding habits, mud crabs were more contaminated compared to tiger prawns sampled from the same sites. Apart from that, the measured levels of Cd, Cr and Pb did not exceed maximum limits for human consumption. Based on the current trend of fish consumption in Tanzania (7.7 kg/person/year), the measured elements (As, Cd, Co, Cu, Mn, Pb and Zn) are not likely to present health risks to shellfish consumers. Nevertheless, potential risks of As and Cu cannot be ruled out if the average per capita consumption is exceeded. This calls for strengthened waste management systems and pollution control measures.

Enhanced weathering of (ultra)basic silicate rocks such as olivine-rich dunite has been proposed as a large-scale climate engineering approach. When implemented in coastal environments, olivine weathering is expected to increase seawater alkalinity, thus resulting in additional CO 2 uptake from the atmosphere. However, the mechanisms of marine olivine weathering and its effect on seawater-carbonate chemistry remain poorly understood. Here, we present results from batch reaction experiments, in which forsteritic olivine was subjected to rotational agitation in different seawater media for periods of days to months. Olivine dissolution caused a significant increase in alkalinity of the seawater with a consequent DIC increase due to CO 2 invasion, thus confirming viability of the basic concept of enhanced silicate weathering. However, our experiments also identified several important challenges with respect to the detailed quantification of the CO 2 sequestration efficiency under field conditions, which include nonstoichiometric dissolution, potential pore water saturation in the seabed, and the potential occurrence of secondary reactions. Before enhanced weathering of olivine in coastal environments can be considered an option for realizing negative CO 2 emissions for climate mitigation purposes, these aspects need further experimental assessment.

The genetic diversity of giant tiger prawns in relation to trace metals (TMs) pollution was analysed using 159 individuals from eight sites at the Tanzanian coast. The seven microsatellites analysed showed high degree of polymorphism (4-44 alleles). The measured genetic diversity (H o =0.592±0.047) was comparable to that of populations in the Western Indian Ocean. Apart from that, correlation analysis revealed significant negative associations between genetic diversity and TMs pollution (p<0.05), supporting the genetic erosion hypothesis. Limited gene flow was indicated by a significant genetic differentiation (F ST =0.059, p<0.05). The Mantel test rejected the isolation-by-distance hypothesis, but revealed that gene flow along the Tanzanian coast is limited by TMs pollution. This suggests that TMs affect larvae settlement and it may account for the measured deficiency of heterozygosity. This calls for strengthened pollution control measures in order to conserve this commercially important species., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Mangroves ecosystems support livelihood and economic activities of coastal communities in the tropics and subtropics. Previous reports have documented the inefficiency of waste treatment facilities in Tanzania to contain trace metals. Therefore, the rapidly expanding coastal population and industrial sector is likely to threaten mangrove ecosystems with metal pollution. This study analysed trace metals in 60 sediment samples and 160 giant tiger prawns from the Tanzanian coast in order to document the distribution of trace metals and to establish if measured levels present a threat to mangrove fauna and are of public health importance. High levels of Cr, Co, Cu, Fe, Mn, Ni, and V was observed in mangroves of river Pangani, Wami, and Rufiji. Multivariate analysis showed that they originate mainly from weathering and erosion in the river catchments. Extreme enrichment of Cd was observed in a mangrove affected by municipal sewage. The distribution of Hg, Pb, and Zn was related with urbanisation and industrial activities along the coast. The metal pollution index was high at Pangani, Saadani, and Rufiji, suggesting that these estuarine mangroves are also affected by human activities in the catchment. Moderate to considerable ecological risks were observed in all sampled mangroves, except for Kilwa Masoko. It was revealed that As, Cd, and Hg present moderate risks to fauna. High levels of Cu, Fe and Zn were observed in prawns but the level of the non-essential Cd, Hg, and Pb did not exceed the maximum allowed levels for human consumption. However, based on the trends of fish consumption in the country, weekly intake of Hg is likely to exceed provisional tolerable weekly intake level, especially in fishing communities. This calls for measures to control Hg emissions and to strengthen sewage and waste treatment in coastal cities and urban centres in the basin of major rivers., (Copyright © 2016 Elsevier Inc. All rights reserved.)

The Diffusive Gradients in Thin Films (DGT) technique using PIWBA resin (The Dow Chemical Company) was developed and validated for the measurement of uranium (U) concentration in natural and uranium mining influenced waters. The U uptake on the PIWBA resin gel was 97.3 ± 0.4% (batch method; Vsol = 5 mL; [U] = 20 μg L(-1); 0.01 M NaNO3; pH = 7.0 ± 0.2). The optimal eluent was found to be HNO3conc/70 °C with an elution efficiency of 88.9 ± 1.4%. The laboratory DGT investigation demonstrated that the PIWBA resin gel exhibits a very good performance across a wide range of pH (3-9) and ionic strength (0.001-0.7 M NaNO3) at different time intervals. Neither effect of PO4(3-) (up to 1.72 × 10(-4) M), nor of HCO3(-) (up to 8.20 × 10(-3) M) on the quantitative measurement of uranium by DGT-PIWBA method were observed. Only at very high Ca(2+) (2.66 × 10(-4) M), and SO4(2-) (5.55 × 10(-4) M) concentration, the U uptake on DGT-PIWBA was appreciably lessened. In-situ DGT field evaluation was carried out in the vicinity of three former uranium mining sites in France (Loire-Atlantique and Herault departments), which employ different water treatment technologies and have different natural geochemical characteristics. There was a similar or inferior U uptake on DGT-Chelex(®)-100 in comparison with the U accumulation on a DGT-PIWBA sampler. Most likely, the performance of Chelex(®)-100 was negatively affected by a highly complex matrix of mining waters. The high concentration and identity of co-accumulating analytes, typical for the mining environment, did not have a substantial impact on the quantitative uptake of labile U species on DGT- PIWBA. The use of the polyphenol impregnated anion exchange resin leads to a significant advancement in the application and development of the DGT technique for determination of U in the vicinity of the former uranium mining sites., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The Diffusive Gradients in Thin films (DGT) technique was used to analyse U, (226)Ra and other trace metals in stream water and soil porewater in a wetland in France impacted by uranium mining. High resolution profiles of metals in soil porewater obtained by DGT could be measured for the first time up to a depth of 75 cm by the construction of a novel DGT holder. In stream water, the DGT technique was compared to speciation carried out by filtration (0.45 μm) and ultrafiltration (UF) (500 kDa/100 kDa/10 kDa) and DGT porewater profiles were compared with piezometer data obtained in a parallel study. An increase in the trace concentrations of dissolved (0.45 μm) and particulate U, (226)Ra, and elements such as Al, Fe, Mn and Ba was observed in the stream water as it passes through the bog as a results of mobilization from the wetland. The porewater results indicate DGT labile metals species to be present in porewater and mobilization of uranium and other elements linked to the presence of enriched clays. In stream water, colloids and particles govern the behavior of U, Al and Fe, whereas Mn, Ba and Ra are essentially transported as truly dissolved metal species with DGT labile concentrations accounting for 100% of the dissolved fraction. The combined approaches of DGT and UF allow us to obtain a better understanding on the biogeochemical processes involved in the retention and mobility of U and (226)Ra in the wetland., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The performance of the Diffusive Gradients in Thin films (DGT) technique with Chelex(®)-100, Metsorb™ and Diphonix(®) as binding phases was evaluated in the vicinity of the former uranium mining sites of Chardon and L'Ecarpière (Loire-Atlantique department in western France). This is the first time that the DGT technique with three different binding agents was employed for the aqueous U determination in the context of uranium mining environments. The fractionation and speciation of uranium were investigated using a multi-methodological approach using filtration (0.45 μm, 0.2 μm), ultrafiltration (500 kDa, 100 kDa and 10 kDa) coupled to geochemical speciation modelling (PhreeQC) and the DGT technique. The ultrafiltration data showed that at each sampling point uranium was present mostly in the 10 kDa truly dissolved fraction and the geochemical modelling speciation calculations indicated that U speciation was markedly predominated by CaUO2(CO3)3(2-). In natural waters, no significant difference was observed in terms of U uptake between Chelex(®)-100 and Metsorb™, while similar or inferior U uptake was observed on Diphonix(®) resin. In turn, at mining influenced sampling spots, the U accumulation on DGT-Diphonix(®) was higher than on DGT-Chelex(®)-100 and DGT-Metsorb™, probably because their performance was disturbed by the extreme composition of the mining waters. The use of Diphonix(®) resin leads to a significant advance in the application and development of the DGT technique for determination of U in mining influenced environments. This investigation demonstrated that such multi-technique approach provides a better picture of U speciation and enables to assess more accurately the potentially bioavailable U pool., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Endocrine disrupting chemicals represent a broad class of compounds, are widespread in the environment and can pose severe health effects. The objective of this study was to investigate the overall estrogen activating potential of PM10 air samples at an urban location with high traffic incidence in Flanders, using a human in vitro cell bioassay. PM10 samples (n = 36) were collected on glass fiber filters every six days between April 2013 and January 2014 using a high-volume sampler. Extraction was executed with a hexane/acetone mixture before analysis using a recombinant estrogen-responsive human ovarian carcinoma (BG1Luc4E2) cell line. In addition, several samples and procedural blanks were extracted with ultra-pure ethanol or acetonitrile to compare extraction efficiencies. Results were expressed as bioanalytical equivalents (BEQs) in femtogram 17β-estradiol equivalent (fg E2-Eq) per cubic meter of air. High fluctuations in estrogenic activity were observed during the entire sampling period, with mean and median BEQs of 50.7 and 35.9 fg E2-Eq m(-)(3), respectively. Estrogenic activity was measured in more than 70% of the samples and several sample extracts showed both high BEQs and high cytotoxicity, which could not be related to black carbon, PM10 or heavy metal concentrations. At this moment, it remains unclear which substances cause this toxicity, but comparison of results obtained with different extraction solvents indicated that acetone/hexane extracts contained more compounds that were cytotoxic and suppressive of responses than those extracted using ultra-pure ethanol. Although more research is needed, the use of a more polar extraction solvent seems to be advisable., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

A new resin- Diphonix(®) in Diffusive Gradients in Thin Films (DGT) technique for the determination of uranium was investigated and compared with previously used binding phases for uranium, Chelex(®)-100 and Metsorb™. The DGT gel preparation and the elution procedure were optimized for the new resin. The U uptake on Diphonix(®) resin gel was 97.4 ± 1.5% (batch method; [U] = 20 μg L(-1); 0.01 M NaNO3; pH = 7.0 ± 0.2). The optimal eluent was found to be 1 M 1-hydroxyethane-1, 1-diphosphonic acid (HEDPA) with an elution efficiency of 80 ± 4.2%. Laboratory DGT study on U accumulation using a DGT samplers with Diphonix(®) resin showed a very good performance across a wide range of pH (3-9) and ionic strength (0.001-0.7 M NaNO3). Diffusion coefficients of uranium at different pH were determined using both, a diffusion cell and the DGT time-series, demonstrating the necessity of the implementation of the effective diffusion coefficients into U-DGT calculations. Diphonix(®) resin gel exhibits greater U capacity than Chelex(®)-100 and Metsorb™ binding phase gels (a Diphonix(®) gel disc is not saturated, even with loading of 10.5 μmol U). Possible interferences with Ca(2+) (up to 1.33 × 10(-2) M), PO4(3-) (up to 1.72 × 10(-4) M), SO4(2-) (up to 4.44 × 10(-3) M) and HCO3(-) (up to 8.20 × 10(-3) M) on U-DGT uptake ([U] = 20 μg L(-1)) were investigated. No effect or minor effect of Ca(2+), PO4(3-), SO4(2-), and HCO3(-) on the quantitative measurement of U by Diphonix(®)-DGT was observed. The results of this study demonstrated the DGT technique with Diphonix(®) resin is a reliable and robust method for the measurement of labile uranium species under laboratory conditions., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Coastal systems act as a boundary between land and sea. Therefore, assessing pollutant concentrations at the coast will provide information on the impact that land-based anthropogenic activities have on marine ecosystems. Sediment and fauna samples from 13 stations along the whole coast of Cameroon were analyzed to assess the level of trace metal pollution in sediments and intertidal fauna. Sediments showed enrichment of As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, V, and Zn. However, pollution of greater concern was observed for Cd, Cr, Cu, Ni, and Zn at the northern stations. Some sites recorded trace metal levels higher than recommended in sediment quality guidelines. Species diversity was low, and high bioaccumulation of trace metals was observed in biological samples. Some edible gastropod species accumulated trace metals above the safety limits of the World Health Organization, European Medicine Agency, and the US Environment Protection Agency. Although industrial pollution is significant along Cameroon's coast, natural pollution from the volcano Mount Cameroon is also of concern.

The Flemish Centre for Environment and Health started with human biomonitoring in 2002 (FLEHS I: 2002-2006). The main goal of the second human biomonitoring cycle (FLEHS II: 2007-2011), was to determine mean values for a large number of pollutants in a representative sample of the general Flemish population. Values for Cd and Pb were updated, and a group of previously undetermined metals and metalloids (As, Mn, Cu and Tl) were included in some of the age groups. In this human biomonitoring program, three different age groups of the general Flemish population were monitored: 255 newborns and their mothers, 210 adolescents aged 14-15, and 204 adults between 20 and 40 years old. Trace elements were determined in cord blood and maternal blood of the mothers, in blood and urine of adolescents and in urine of adults. Determinants of life-style and personal factors were taken into account. The levels of trace elements in cord blood and maternal blood were for most elements at the lower end of the range found in literature. For Pb, As and Tl, a strong correlation (respectively r=0.43, 0.55 and 0.33; p<0.05) was found between levels in cord blood (respectively 8.6, 0.54 and 0.017 μg/L) and maternal blood (11.1, 0.64 and 0.028 μg/L), indicating that they are transported via the placenta from mother to fetus. The levels found in the adolescents and adults were compared with results from international biomonitoring studies, and were found to be in the same ranges. With the exception of Pb, all trace elements increased with increasing age group population. Finally, the results also showed that the levels of Cd and Pb in blood for this campaign (e.g. for Pb 8.6 and 14.8 μg/L in neonates and adolescents respectively) were lower compared to the first campaign (e.g. for Pb 14.7 and 21.7 μg/L in neonates and adolescents respectively), indicating a decrease over time. However, differences in sampling strategies might partially explain this observed trend., (Copyright © 2014 Elsevier GmbH. All rights reserved.)

Predicting metal concentrations in surface waters is an important step in the understanding and ultimately the assessment of the ecological risk associated with metal contamination. In terms of risk an essential piece of information is the accurate knowledge of the partitioning of the metals between the dissolved and particulate phases, as the former species are generally regarded as the most bioavailable and thus harmful form. As a first step towards the understanding and prediction of metal speciation in the Scheldt Estuary (Belgium, the Netherlands), we carried out a detailed analysis of a historical dataset covering the period 1982-2011. This study reports on the results for two selected metals: Cu and Cd. Data analysis revealed that both the total metal concentration and the metal partitioning coefficient (Kd) could be predicted using relatively simple empirical functions of environmental variables such as salinity and suspended particulate matter concentration (SPM). The validity of these functions has been assessed by their application to salinity and SPM fields simulated by the hydro-environmental model SLIM. The high-resolution total and dissolved metal concentrations reconstructed using this approach, compared surprisingly well with an independent set of validation measurements. These first results from the combined mechanistic-empirical model approach suggest that it may be an interesting tool for risk assessment studies, e.g. to help identify conditions associated with elevated (dissolved) metal concentrations., (Copyright © 2013 Elsevier B.V. All rights reserved.)

In the Flemish human biomonitoring programme FLEHS II (2007-2011) trace metals (Cd, Pb, Cr, Ni, Cu, Mn, Tl, Sb, As and toxic relevant arsenic) were analysed in the blood and urine of adolescents (14-15 years old) in the reference population in Flanders and in areas of important industrial activities: Genk-Zuid and Menen. After adjustment of the results for confounding factors, the adolescents living in Genk-Zuid had higher levels of Cr, Cu and Tl in blood, higher levels of Cd and toxic relevant arsenic (TRA) in urine, but lower levels of Ni in blood and Sb in urine compared to the reference population. In Menen higher levels of Cd and Cu in urine, higher concentrations of Tl in blood but lower concentrations of Pb in blood and lower Ni, Sb and As in urine were found compared to the reference population. For both the reference population and the hot spots the concentrations are within the ranges found in other countries. Compared to the previous biomonitoring programme FLEHS I (2002-2006) a decrease in the concentrations of Cd and especially of Pb in blood was observed. However, it cannot be excluded that differences between the two campaigns are partially due to different sampling strategies., (Copyright © 2013 Elsevier GmbH. All rights reserved.)

The accumulation of trace elements (Mg, Mn, Sr, Ba) in Unio pictorum L. mussel shells from Lake Balaton has been assessed using a Laser Ablation (LA) system coupled to either a quadrupole-based or a sector-field inductively coupled plasma-mass spectrometer (ICP - MS), as well as by a combination of micro-drill sampling and solution ICP-MS. The LA-ICP-MS measurements were carried out in the holes made by the micro-drilling system. The longitudinal concentration profiles obtained with the different methods show similar patterns. However, the absolute concentrations determined at individual spots (holes) can be quite different. Especially Ba shows erratic peaks at a very small spatial scale. A paired, two-sample t-test between LA-ICP-MS longitudinal profiles and between LA-ICP-MS and micro-drill/solution ICP-MS profiles indicates that, in most cases, there is no significant difference between the concentration profiles of Ba, Mg, Mn and Sr. Average shell concentrations of Mg, Mn, Sr and Ba, as obtained by LA-ICP-MS and micro-drill/solution ICP-MS, compare well with bulk shell concentrations as obtained by acid digestion/ICP-MS of larger shell pieces. Next to the four elements mentioned above, also the concentrations of Cd, Co, Cr, Cu, Ni, Pb and Zn could be determined by bulk shell analysis. The element concentrations in 11 shells, all sampled at the same site, show a relative standard deviation (RSD) between 2% (Ni) and 46% (Zn). LA-ICP-MS and micro-drill solution ICP-MS are not sensitive enough for the determination of ultra-trace elements in Lake Balaton's mussel shells. We estimated the amount of shell material necessary to determine Ni, Pb, Cr and Cu by micro-drilling ICP-MS (for a concentration that equals 3 times their limit of detection) at, respectively, 0.04, 0.82, 2.7 and 0.4 mg, while the amount sampled by micro-drilling is about 0.06 mg., (© 2013 Elsevier B.V. All rights reserved.)

Muddy sediments of the Belgian Continental Zone (BCZ) are contaminated by metals such as Co, As, Cd, Pb, and Ni. Previous studies have suggested that mineralization of phytodetritus accumulating each year on sediments might cause secondary contaminations of the overlying seawater (metal effluxes). The aim of the present research was to investigate these effluxes using a microcosm approach. Muddy sediments were placed in microcosms (diameter: 15 cm) and overlaid by phytodetritus (a mix of Phaeocystis globosa with the diatom Skeletonema costatum). The final suspension was 130.6 mg L(-1) (dw) and the final chlorophyll a content was 750 ± 35 μg L(-1) (mean ± SD). Natural seawater was used for controls. Microcosms were then incubated in the dark at 15°C during 7 days. Metals were monitored in overlying waters and microbial communities were followed using bacterial and nanoflagellate DAPI counts, thymidine incorporation, community level physiological profiling (CLPP) and fluorescein diacetate analysis (FDA). Benthic effluxes observed in sediments exposed to phytodetritus were always more elevated than those observed in controls. Large effluxes were observed for Mn, Co and As, reaching 1084 nmol m(-2)day(-1) (As), 512 nmol m(-2)day(-1) (Co), and 755 μmol m(-2)day(-1) (Mn). A clear link was established between heterotrophic microbial activity and metal effluxes. The onset of mineralization was very fast and started within 2h of deposition as revealed by CLPP. An increased bacterial production was observed after two days (8.7 mg Cm(-2)day(-2)) and the bacterial biomass appeared controlled by heterotrophic nanoflagellates. Calculations suggest that during phytoplankton blooms the microbial activity alone may release substantial amounts of dissolved arsenic in areas of the BCZ covered by muddy sediments., (Copyright © 2011 Elsevier B.V. All rights reserved.)

The influence of trace metal pollution on the community structure of soft bottom molluscs was investigated in intertidal areas of the Dar es Salaam coast. Significant enrichment of As, Mn, Mo, Sb, and Zn in sediments was recorded. Redundancy analysis indicated that trace metal pollution contributed 68% of the variation in community structure. Monte Carlo permutation test showed that As and Sb contributed significantly to variation in species composition. T-value biplots and van Dobben circles showed that the gastropods Acteon fortis, Assiminea ovata, and Littoraria aberrans, were negatively affected by As and Sb, while the bivalve Semele radiata and the gastropod Conus litteratus were only negatively affected by As. Bioaccumulation of As, Cd, Cu, Mo and Zn occurred in the bivalve Mactra ovalina and the gastropod Polinices mammilla. This calls for regular monitoring and management measures., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Our current view about the relationship between metals and bacteria in marine sediments might be biased because most studies only use ex situ approaches to quantify metals. The aim of the present research was to compare ex situ and in situ methods of metal measurement (DET and DGT--diffusive equilibration or diffusive gradients in thin-films) and relate the results with two commonly used microbiological variables (bacterial biomass and bacterial diversity as revealed by DGGE). No previous studies have used such in situ approaches in microbial ecology. For biomass and most of the investigated trace metals (Ag, Cd, Sn, Cr, Ni, Cu, Pb, and Al) no significant correlations were found. The exceptions were Fe, Mn, Co, and As which behave like micronutrients. For bacterial diversity, no relevant relationships were found. We conclude that in situ methods are more adapted tools for microbial ecologists but that ex situ approaches are still necessary., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

3-Mercaptopropyl functionalized SBA-15 (SH-SBA) and 3-mercaptopropyl functionalized ethenylene bridged periodic mesoporous organosilica (SH-PMO) were included in a Diffusive Gradients in Thin film (DGT) probe and compared to similar commercially available resins also containing thiol functional groups, such as Sumichelate Q10R (SQR) and 3-mercaptopropyl functionalized silica gel (SH-KG), and also to the Chelex-100 resin for the determination of labile Hg concentrations. An agarose gel was used as the diffusive gel because the classic polyacrylamide gel shows more than 20% of Hg adsorption. According to our results, the Chelex-100 resin presents a much lower affinity for Hg than the thiol based resins. The non-linear accumulation profile of mercury with time for the Chelex-100 resin makes it in fact impossible to use Fick's law for estimating the diffusion coefficient of Hg. The 4 other resins all show a linear accumulation profile of Hg with time. Although the highest accumulation rate is observed for SH-PMO followed by SQR, SH-SBA and SH-KG, these values do not differ very much., (Copyright © 2011 Elsevier B.V. All rights reserved.)

PAHs, PCDD/Fs and non-ortho PCBs have been assessed in Yser and Upper-Scheldt river sediments. Higher contamination levels were observed in the Upper-Scheldt sediments: maximum concentrations for the 16 US-EPA PAHs, PCDD/Fs and non-ortho PCBs respectively amount to 8.9 mg kg(-1), 12 ng TEQ kg(-1) and 5.1 ng TEQ kg(-1). Diagnostic PAH ratios in sediments and atmospheric samples suggest that the PAH compounds are from pyrolytic origin, more specifically combustion processes. The huge consumption of coal in cokes-ovens and smelters and its use for house-heating in Northern France, although decreasing during the last decades, are in support of that suggestion. PCDD/F fingerprints in sediments and deposition material indicate that OCDD is the dominant congener. In addition use of pentachlorophenol (PCP) in the past led to a minor contribution of PCDD/Fs in our sediment samples. Non-ortho PCBs form a substantial fraction of the total TEQ concentrations observed in the sediments. Since the 1980s and 1990s a substantial reduction of the PCDD/F sediment concentrations is observed, but this is not the case for the PAHs., (Copyright © 2011 Elsevier Ltd. All rights reserved.)