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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 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.)

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.)

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 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.)

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.)

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 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.)

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.)

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.)

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.)

Correlations between trace metals in dissolved and particulate phases, zooplankton, mussels and sediments in Lake Balaton were investigated. The degree of correlation between the various metals was different in each of the investigated compartments. Particulate metal concentrations (microg g(-1)) were anti-correlated with suspended particulate matter (SPM) (mg l(-1)), indicating a dilution effect, while total metal concentrations in the water column (microg l(-1)) were highly correlated with SPM, implying a major influence of the turbidity on the total metal concentrations. Between compartments, not many significant correlations were recognized. Only Ba, Ca, Sr and Mg are correlated in the sediments and in the particulate phase, suggesting common sources for both compartments. Partitioning coefficients (Kd) of trace metals between dissolved and particulate phases are generally low, typical for natural water and fairly stable over the lake. Most of the trace metals (Zn, Co, Cd and Pb) exist in the particulate phase (for about 70% of the total metal load). Cu and Ni are exceptions, showing a more equal distribution. Bioconcentration factors (BCF) of zooplankton and mussels were comparable to those of other natural waters. A negative biomagnification from suspended particulate matter to zooplankton and from sediment to mussel was recognized for all trace metals, except a small enrichment of Zn in zooplankton and Cd in mussel. Four factors were recognized in SPM and in sediments but they did not contain the same group of metals. Cluster analysis showed that metal accumulations in the sediments were different between northern and southern shores and in SPM between western and eastern areas.