Microplastics (≤ 10 µm) bioaccumulation in marine sponges along the Moroccan Mediterranean coast: Insights into species-specific distribution and potential bioindication.

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 3.95×105 to 1.05×106 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.

Methionine sulfoxide reductase B from Corynebacterium diphtheriae catalyzes sulfoxide reduction via an intramolecular disulfide cascade.

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 Zn2+, 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.

Olivine Dissolution in Seawater: Implications for CO2 Sequestration through Enhanced Weathering in Coastal Environments.

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 CO2 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 CO2 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 CO2 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 CO2 emissions for climate mitigation purposes, these aspects need further experimental assessment.

Bioaccumulation and public health implications of trace metals in edible tissues of the crustaceans Scylla serrata and Penaeus monodon from the Tanzanian coast.

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.

Trace metals in the giant tiger prawn Penaeus monodon and mangrove sediments of the Tanzania coast: Is there a risk to marine fauna and public health?

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.

Assessment of trace metal pollution in sediments and intertidal fauna at the coast of Cameroon.

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.

Mercury distribution, mobilization and bioavailability in polluted sediments of Scheldt Estuary and Belgian Coastal Zone.

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 (HgLA) were mostly lower than the porewater Hg concentrations (HgPW), 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.

Origin and partitioning of mercury in the polluted Scheldt Estuary and adjacent coastal zone.

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 ([HgSPM]) progressively decreased with increasing salinity and was strongly correlated with organic matter content (%Corg) and origin (identified with δ13Corg). While [HgSPM] drives total Hg concentration in the estuary (total dissolved Hg, HgTD 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 HgTD (40 ± 21 %) and the majority of this HgTD was reducible (i.e. labile Hg), meaning potentially available for microorganisms. Compared to the '90s, a significant decrease of [HgSPM] was observed in the estuary, but this was not the case for [HgTD], 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.

Assessment of 226Ra and U colloidal transport in a mining environment.

The colloidal transport of trace (Fe, Al, Ba, Pb, Sr, U) and ultra-trace (226Ra) 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 226Ra 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 226Ra 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 226Ra concentration. The distribution of 226Ra between the truly dissolved and colloidal fractions was accurately reproduced using a (Rax,Ba1-x)SO4 solid solution, with values of the Guggenheim parameter a0 close to ideality. 226Ra 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.

Investigation on metal geochemical cycling in an anthropogenically impacted tidal river in Belgium.

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.

Diffusive Gradients in Thin-films technique for uranium monitoring along a salinity gradient: A comparative study on the performance of Chelex-100, Dow-PIWBA, Diphonix, and Lewatit FO 36 resin gels in the Scheldt estuary.

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 UO2(CO3)34- (from 2 to 14%) towards the mouth.

Insights into bioaccumulation and bioconcentration of potentially toxic elements in marine sponges from the Northwestern Mediterranean coast of Morocco.

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.

A multimethodological evaluation of arsenic in the Zenne River, Belgium: Sources, distribution, geochemistry, and bioavailability.

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 ZrO2) 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.

Cable Bacteria Activity Modulates Arsenic Release From Sediments in a Seasonally Hypoxic Marine Basin.

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.

Naturally occurring potentially toxic elements in groundwater from the volcanic landscape around Mount Meru, Arusha, Tanzania and their potential health hazard.

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.

Elimination of interferences in the determination of platinum, palladium and rhodium by diffusive gradients in thin films (DGT) and inductively coupled plasma mass spectrometry (ICP MS) using selective elution.

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 H2SO4 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.

Simultaneous determination of arsenic and uranium by the diffusive gradients in thin films technique using Lewatit FO 36: Optimization of elution protocol.

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.

Speciation of Inorganic Compounds in Aquatic Systems Using Diffusive Gradients in Thin-Films: A Review.

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.

Cysteine-modified silica resin in DGT samplers for mercury and trace metals assessment.

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.

Distribution of platinum (Pt), palladium (Pd), and rhodium (Rh) in urban tributaries of the Scheldt River assessed by diffusive gradients in thin films technique (DGT).

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.