Diffusive Gradients In Thin Films Samplers Research Articles

Simultaneous measurement of labile U(VI) concentration and (234U/238U) activity ratio using a Monophos®-based Diffusive Gradients in thin-films sampler

BackgroundIn a context of environmental monitoring around installations related to the nuclear fuel cycle, the Diffusive Gradient in Thin-films (DGT) technique captures the integrated concentration of U isotopes in their native environment, yielding comprehensive data on U origin (anthropogenic vs natural), total concentration, and mobility. However, for common deployment times (4–5 days) in moderately basic waters, none of the commercially available binding gels is adapted to measure the total U concentration. So, the development of novel DGT binding gels is timely. ResultsA new DGT sampler, using the Monophos® resin, as well as a new model for the interpretation of the DGT flux, has been successfully developed to measure the labile U concentration (which was also its total concentration) in moderately basic waters (pH ≈ 8). The model accounts for the penetration of uranyl carbonate complexes into the binding gel. Monophos-DGT samplers were able to quantify the total U concentration (accuracy >90 %) in three different mineral basic waters and in a synthetic seawater in laboratory experiments, as well as in situ in the rivers Essonne and Œuf, France. Ion interferences (e.g., Ca2+, Mg2+ and HCO3−), critical when using Chelex and Metsorb resins as binding agents, were overcome by using the new DGT sampler, thus allowing for a longer linear accumulation of U in the tested matrices and, above all, a better detection of U minor isotopes improving the potential of using DGT samplers for water source tracing through isotopic measurements. SignificanceThe use of the new DGT sampler and the new model for the interpretation of DGT flux is recommended to improve the accuracy of total U concentration determinations in field applications. Moreover, simultaneous elemental and isotopic measurements were successfully performed during field application, confirming new perspectives for environmental applications such as identification of U pollution sources by using isotopic signatures.

On-site evaluation of DGT passive sampling for quantitatively measuring per- and polyfluoroalkyl substances in a river-estuary-sea water system

The passive sampling technique of diffusive gradients in thin-films (DGT) is promising for monitoring emerging contaminants such as per- and polyfluoroalkyl substances (PFAS). It is urgent to evaluate the impacts of salinity and exposure time on DGT sampling before it can be set as a standard method. Herein, DGT sampler based on the binding gel of weak anion exchanger (WAX) resin was deployed in a representative water system of the Xiaoqing river-estuary-sea for representative sampling windows (<1 day to 28 days) with high pH (8.18 ± 0.04 to 8.51 ± 0.17) and wide ranges of salinity (0.95 ± 0.07‰ to 14.37 ± 3.92‰), total dissolved solids (1.20 ± 0.09 g/L to 15.29 ± 3.91 g/L) and dissolved organic matter (2.8–32 mg/L). The results showed that the WAX-DGT sampler exhibited good performance for most target PFAS except for short-chain perfluorocarboxylates (C ≤ 5) in 14 days. When the exposure time was over 14 days, biofouling of the sampler may deflect the mass accumulation of the PFAS in the sampler. Salinity played an important role in the mass binding of PFAS by DGT. The shorter the carbon chain of the compound, the greater the influence of the salinity. PFAS with carboxyl groups had greater affinities for the biofouled membrane filter than those with sulfonic groups. In the river-estuary-sea system, where PFAS concentrations changed dynamically, the temporal resolution of the monitoring strategy has been demonstrated to be more important than spatial resolution. DGT provided a better integral of PFAS exposure than grab sampling in the dynamic water system and offered equivalent sensitivity of grab sampling with exposure time <10 d and greater sensitivity with exposure time ≥10 d. Thus, DGT has the advantage of providing high temporal resolution monitoring. This study provided support for the standardization of the DGT technique.

Development of diffusive gradients in thin-films technique for monitoring polycyclic aromatic hydrocarbons in coastal waters

Addressing the challenge of accurately monitoring polycyclic aromatic hydrocarbons (PAHs) in aquatic systems, this study employed diffusive gradients in thin-films (DGT) technique to achieve methods detection limits as low as 0.02 ng L−1 to 0.05 ng L−1 through in situ preconcentration and determination of time-integrated concentrations. The efficacy of the developed DGT samplers was validated under diverse environmental conditions, demonstrating independence from factors such as pH (5.03–9.01), dissolved organic matter (0–20 mg L−1), and ionic strength (0.0001–0.6 M). Notably, the introduction of a novel theoretical approach to calculate diffusion coefficients based on solvent-accessible volume tailored for PAHs significantly enhanced the method’s applicability, particularly for organic pollutants with low solubility. Field deployments in coastal zones validated the DGT method against traditional grab sampling, with findings advocating a 4 to 7-day optimal deployment duration for balancing sensitivity and mitigating lag time effects. These results provide a sophisticated, efficient solution to the persistent challenge of monitoring hydrophobic organic pollutants in aquatic environments, broadening the scope and applicability of DGT in environmental science and providing a robust tool for researchers.

Distribution and Homogenization of Multiple Mercury Species Inputs to Freshwater Wetland Mesocosms.

Mercury (Hg)-impaired aquatic ecosystems often receive multiple inputs of different Hg species with varying potentials for transformation and bioaccumulation. Over time, these distinct input pools of Hg homogenize in their relative distributions and bioaccumulation potentials as a result of biogeochemical processes and other aging processes within the ecosystem. This study sought to evaluate the relative time scale for homogenization of multiple Hg inputs to wetlands, information that is relevant for ecosystem management strategies that consider Hg source apportionment. We performed experiments in simulated freshwater wetland mesocosms that were dosed with four isotopically labeled mercury forms: two dissolved forms (Hg2+ and Hg-humic acid) and two particulate forms (nano-HgS and Hg adsorbed to FeS). Over the course of one year, we monitored the four Hg isotope endmembers for their relative distribution between surface water, sediment, and fish in the mesocosms, partitioning between soluble and particulate forms, and conversion to methylated mercury (MeHg). We also evaluated the reactivity and mobility of Hg through sequential selective extractions of sediment and the uptake flux of aqueous Hg in a diffusive gradient in thin-film (DGT) passive samplers. We observed that the four isotope spikes were relatively similar in surface water concentration (ca. 3000 ng/L) immediately after spike addition. At 1-3 months after dosing, Hg concentrations were 1-50 ng/L and were greater for the initially dissolved isotope endmembers than the initially particulate endmembers. In contrast, the Hg isotope endmembers in surface sediments were similar in relative concentration within 2 months after spike addition. However, the uptake fluxes of Hg in DGT samplers, deployed in both the water column and surface sediment, were generally greater for initially dissolved Hg endmembers and lower for initially particulate endmembers. At one year postdosing, the DGT-uptake fluxes were converging toward similar values between the Hg isotope endmembers. However, the relative distribution of isotope endmembers was still significantly different in both the water column and sediment (p < 0.01 according to one-way ANOVA analysis). In contrast, selective sequential extractions resulted in a homogeneous distribution, with >90% of each endmember extracted in the KOH fraction, suggesting that Hg species were associated with sediment organic matter. For MeHg concentrations in surface sediment and fish, the relative contributions from each endmember were significantly different at all sampling time points. Altogether, these results provide insights into the time scales of distribution for different Hg species that enter a wetland ecosystem. While these inputs attain homogeneity in concentration in primary storage compartments (i.e., sediments) within weeks after addition, these input pools remain differentiated for more than one year in terms of reactivity for passive samplers, MeHg concentration, and bioaccumulation.

Development of diffusive gradients in thin film technique for seasonal monitoring of benzophenone-type UV filters in coastal waters

Benzophenone(BP)-type UV filters are continuously released into various aquatic environments via the effluent discharge of wastewater treatment plants (WWTPs) and recreational activities in coastal beaches. In this study, we developed a robust and reliable sampling approach, diffusive gradients in thin-films (DGT), for seasonal monitoring of six BP derivatives in coastal waters to investigate their occurrence and environmental risk. The binding capacities of both XAD-2 and HLB gels for test BPs were over 252 μg with no significant deterioration in marine environment, suggesting that theoretically, DGT is capable of sampling for at least 3 months effectively. The diffusion coefficients of BPs in freshwater and seawater were determined for the first time. The sampling performance showed no dependence on environmental conditions including pH (4.0–8.5), ionic strength (0.0001–0.5 M) and dissolved organic matter (0–20 mg L−1). The developed DGT samplers were successfully applied in a river estuary linked to a WWTP and a bathing beach at different periods of one year. Results showed that the concentrations of BPs in the coastal waters were dependent on seasonal variation. The highest level in summer and the ecological risk should be considered based on the risk quotient values. These results demonstrated that the present DGT method is suitable for measuring, characterization, and risk assessment of BPs in freshwater and marine environment.

Utility of Diffusive Gradient in Thin-Film Passive Samplers for Predicting Mercury Methylation Potential and Bioaccumulation in Freshwater Wetlands.

Mercury is a risk in aquatic ecosystems when the metal is converted to methylmercury (MeHg) and subsequently bioaccumulates in aquatic food webs. This risk can be difficult to manage because of the complexity of biogeochemical processes for mercury and the need for accessible techniques to navigate this complexity. Here, we explored the use of diffusive gradient in thin-film (DGT) passive samplers as a tool to simultaneously quantify the methylation potential of inorganic Hg (IHg) and the bioaccumulation potential of MeHg in freshwater wetlands. Outdoor freshwater wetland mesocosms were amended with four isotopically labeled and geochemically relevant IHg forms that represent a range of methylation potentials (202Hg2+, 201Hg-humic acid, 199Hg-sorbed to FeS, and 200HgS nanoparticles). Six weeks after the spikes, we deployed DGT samplers in the mesocosm water and sediments, evaluated DGT-uptake rates of total Hg, MeHg, and IHg (calculated by difference) for the Hg isotope spikes, and examined correlations with total Hg, MeHg, and IHg concentrations in sediment, water, and micro and macrofauna in the ecosystem. In the sediments, we observed greater relative MeHg concentrations from the initially dissolved IHg isotope spikes and lower MeHg levels from the initially particulate IHg spikes. These trends were consistent with uptake flux of IHg into DGTs deployed in surface sediments. Moreover, we observed correlations between total Hg-DGT uptake flux and MeHg levels in periphyton biofilms, submergent plant stems, snails, and mosquitofish in the ecosystem. These correlations were better for DGTs deployed in the water column compared to DGTs in the sediments, suggesting the importance of vertical distribution of bioavailable MeHg in relation to food sources for macrofauna. Overall, these results demonstrate that DGT passive samplers are a relatively simple and efficient tool for predicting IHg methylation and MeHg bioaccumulation potentials without the need to explicitly delineate IHg and MeHg speciation and partitioning in complex ecosystems.

Development and evaluation of a ceramic diffusive layer based DGT technique for measuring organic micropollutants in seawaters.

Diffusive gradients in thin-films (DGT) technique has been well demonstrated as a robust tool for measuring organic micropollutants (OMPs) in the aquatic environment. However, potential adsorption of the OMPs on organic polymer filters and flow rate of waters can affect the measuring results of the DGT method, hence tedious work should be conducted to reduce these interferences. In the present study, a novel DGT technique coupled with a ceramic diffusive layer was developed to measure the OMPs in seawaters. The ceramic diffusive layer exhibited adsorption inertness to the OMPs with various logKow values. Moreover, the ceramic diffusive layer based DGT technique was proved to be less affected by the flow rate than the traditional DGT with agarose diffusive layer. The developed DGT device exhibited kinetic accumulation for the targets during a 6-d deployment, and measurement of the OMPs by the DGT method was independent with pH and ionic strength. Finally, the developed DGT sampler was applied in coastal waters of Dalian, and eight OMPs were detected with levels ranging from 1.58 to 13.1ng/L. The development of the ceramic diffusive membrane can lead to simplification of the DGT applications, promoting the progress of the OMPs monitoring technology.

Development and Applications of Novel DGT Passive Samplers for Measuring 12 Per- and Polyfluoroalkyl Substances in Natural Waters and Wastewaters.

Extensive and long-term use of per- and polyfluoroalkyl substances (PFASs) has caused their widespread distribution in aquatic systems. A new diffusive gradients in thin-films (DGT) passive sampling method based on weak anion exchanger (WAX) binding layer is developed here for monitoring five perfluoroalkyl carboxylic acids (PFCAs), five perfluoroalkanesulfonic acids (PFSAs) and two PFASs (6:2 FTSA and GenX) in waters. Performance of WAX-DGTs was independent of environmental conditions, namely pH (3.03-8.96), ionic strength (1-500 mM), and DOM content (4-30 mg L-1). Diffusion coefficients (D) of the 12 PFASs in the diffusive gels were measured, 9 for the first time. Linear correlations between D and perfluoroalkyl chain lengths (CF2) were established to obtain D for congener chemicals with the similar functional group and structure. The binding capacity of the WAX-DGT sampler was at least 440 μg PFASs per sampler, sufficient for applications in waters across a wide range of conditions and PFASs concentrations. Successful applications of WAX based DGT samplers in a wastewater treatment plant (WWTP) and three rivers has demonstrated that DGT is a powerful tool for monitoring, surveillance and research of these 12 PFASs in aquatic systems, and can be extended to wider suites of PFs in future.

Development and evaluation of a DGT sampler using functionalised cross-linked polyethyleimine for the monitoring of arsenic and selenium in mine impacted wetlands

Arsenic and selenium are both carcinogenic and their presence in fresh water has attracted the development of robust and accurate monitoring techniques. A new diffusive gradients in thin-films (DGT) sampler was developed and evaluated for the in situ measurements of arsenic and selenium. The binding layer was made from a mixture of sulphonated and phosphonated cross-linked polyethylenimine (SCPEI and PCPEI, respectively). The optimum ratio of a SCPEI and PCPEI resin mixture was determined. The DGT sampler was calibrated under laboratory conditions to determine the influence of sample turbulence, concentration and pH. The optimised DGT passive sampler was field deployed in a mine impacted dam for 12 days. Binding layer optimisation shows that the polymers had to be mixed in a specific ratio of 80% sulphonated and 20% phosphonated per 0.8 g of the resin mixture, in the loose polymer form. Embedding the resin mixture in agarose gel reduced the uptake of both arsenic and selenium dramatically. At sample pH 3.0 and 5.0, the DGT sampler did not show significant differences in uptake of the two elements during the 15 day deployment. The passive sampler had limited adsorption capacity and was found better suited for dilute solutions, with concentrations below 0.5 mg L−1 of the target metals. This effect was more pronounced when exposed to dam water which had competing cations. Cations may have reduced the capacity by binding to the PEI backbone via the large number of amine groups. Nonetheless, these cations did not show linear uptake.

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.

Assessing the Risk of Metals and Their Mixtures in the Antarctic Nearshore Marine Environment with Diffusive Gradients in Thin-Films.

Robust environmental assessments and contaminant monitoring in Antarctic near-shore marine environments need new techniques to overcome challenges presented by a highly dynamic environment. This study outlines an approach for contaminant monitoring and risk assessment in Antarctic marine conditions using diffusive gradients in thin-films (DGT) coupled to regionally specific ecotoxicology data and environmental quality standards. This is demonstrated in a field study where DGT samplers were deployed in the near-shore marine environment of East Antarctica around the operational Casey station and the abandoned Wilkes station to measure the time-averaged biologically available fraction of metal contaminants. The incorporation of DGT-labile concentrations to reference toxicity mixture models for three Antarctic organisms predicted low toxic effects (<5% effect to the growth or development of each organism). The comparison of metal concentrations to the Australian and New Zealand default water quality guideline values (WQGVs) showed no marine site exceeding the WQGVs for 95% species protection. However, all sites exceeded the 99% WQGVs due to copper concentrations that are likely of geogenic origin (i.e., not from anthropogenic sources). This study provides evidence supporting the use of the DGT technique to monitor contaminants and assess their environmental risk in the near-shore marine environment of Antarctica.

In situ measurement of perfluoroalkyl substances in aquatic systems using diffusive gradients in thin-films technique

To better understand the environmental impact of ubiquitous perfluoroalkyl substances (PFASs) in waters, reliable and robust measurement techniques are needed. As one of the most widely used passive sampling approaches, diffusive gradients in thin-films (DGT) is not only easy to handle but also provides time-weighted analyte concentrations. Based on DGT with XAD18 as a binding agent, we developed a new methodology to measure two frequently detected PFASs in surface waters and wastewaters, i.e. perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Their diffusion coefficients in the diffusive gel, measured using an independent diffusion cell, were 4.37 × 10−6 and 5.08 × 10−6 cm2 s−1 at 25 °C, respectively. DGT had a high capacity for PFOA and PFOS at 196 and 246 μg per gel disk, suggesting the DGT sampler was suitable for deployment of several weeks. Time-integrated concentrations of PFOA and PFOS in a natural lake and river, and a municipal wastewater treatment plant effluent using DGT samplers deployed in situ for 12–33 d were comparable to those measured by a solid-phase extraction method coupled with high-frequency grab sampling. This study demonstrates that DGT is an effective tool for in situ monitoring of PFASs in natural waters and wastewaters.

Diffusive gradients in thin-films (DGT) for in situ sampling of selected endocrine disrupting chemicals (EDCs) in waters

A passive water sampler based on the diffusive gradients in thin-films (DGT) technique was developed and tested for 3 groups of endocrine disrupting chemicals (EDCs, including oestrogens, alkyl-phenols and bisphenols). Three different resins (hydrophilic-lipophilic-balanced (HLB), XAD18 and Strata-XL-A (SXLA)) were investigated for their suitability as the binding phase for DGT devices. Laboratory tests across a range of pH (3.5–9.5), ionic strength (0.001–0.5 M) and dissolved organic matter concentration (0–20 mg L−1) showed HLB and XAD18-DGT devices were more stable compared to SXLA-DGT. HLB-DGT and XAD18-DGT accumulated test chemicals with time consistent with theoretical predictions, while SXLA-DGT accumulated reduced amounts of chemical. DGT performance was also compared in field deployments up to 28 days, alongside conventional active sampling at a wastewater treatment plant. Uptake was linear to the samplers over 18 days, and then began to plateau/decline, indicating the maximum deployment time in those conditions. Concentrations provided by the DGT samplers compared well with those provided by auto-samplers. DGT integrated concentrations over the deployment period in a way that grab-sampling cannot. The advantages of the DGT sampler over active sampling include: low cost, ease of simultaneous multi-site deployment, in situ analyte pre-concentration and reduction of matrix interferences compared with conventional methods. Compared to other passive sampler designs, DGT uptake is independent of flow rate and therefore allows direct derivation of field concentrations from measured compound diffusion coefficients. This passive DGT sampler therefore constitutes a viable and attractive alternative to conventional grab and active water sampling for routine monitoring of selected EDCs.

Investigation and application of diffusive gradients in thin-films technique for measuring endocrine disrupting chemicals in seawaters

Endocrine disrupting chemicals (EDCs) can be released to coastal waters and affect the endocrine system of marine organisms. To monitor their levels in seawaters, a simple, robust passive sampling method, the diffusive gradients in thin-films (DGT) technique, was developed with XDA-1 resin as a binding agent. Six EDCs (including three estrogens, two pesticides and bisphenol A) were used to assess the performance of the DGT. The XDA-1 binding gel showed adequate ability for adsorbing EDCs in seawaters. The DGT sampler exhibited linear accumulation for the EDCs during a 15-day deployment and diffusion coefficients and sampling rates were calculated. The DGT measurement was independent of pH in the range 7.0–9.0 and ionic strength in the range 0.4–0.8 M. Field applications of this DGT in a coast of Dalian (China) showed comparable results to those from grab sampling. Five EDCs were detected with concentrations ranging from 0.7 to 19.4 ng L−1. This study is a first attempt to apply DGT sampler for determining EDCs in seawaters.

Influence of Sulfide Nanoparticles on Dissolved Mercury and Zinc Quantification by Diffusive Gradient in Thin-Film Passive Samplers.

Diffusive gradient in thin-film (DGT) passive samplers are frequently used to monitor the concentrations of metals such as mercury and zinc in sediments and other aquatic environments. The application of these samplers generally presumes that they quantify only the dissolved fraction and not particle-bound metal species that are too large to migrate into the sampler. However, metals associated with very small nanoparticles (smaller than the pore size of DGT samplers) can be abundant in certain environments, yet the implications of these nanoparticles for DGT measurements are unclear. The objective of this study was to determine how the performance of the DGT sampler is affected by the presence of nanoparticulate species of Hg and Zn. DGT samplers were exposed to solutions containing known amounts of dissolved Hg(II) and nanoparticulate HgS (or dissolved Zn(II) and nanoparticulate ZnS). The amounts of Hg and Zn accumulated onto the DGT samplers were quantified over hours to days, and the rates of diffusion of the dissolved metal (i.e., the effective diffusion coefficient D) into the sampler's diffusion layer were calculated and compared for solutions containing varying concentrations of nanoparticles. The results suggested that the nanoparticles deposited on the surface of the samplers might have acted as sorbents, slowing the migration of the dissolved species into the samplers. The consequence was that the DGT sampler data underestimated the dissolved metal concentration in the solution. In addition, X-ray absorption spectroscopy was employed to determine the speciation of the Hg accumulated on the sampler binding layer, and the results indicated that HgS nanoparticles did not appear to directly contribute to the DGT measurement. Overall, our findings suggest that the deployment of DGT samplers in settings where nanoparticles are relevant (e.g., sediments) may result in DGT data that incorrectly estimated the dissolved metal concentrations. Models for metal uptake into the sampler may need to be reconsidered.

Measurement of dissolved reactive phosphorus in water with polyquaternary ammonium salt as a binding agent in diffusive gradients in thin-films technique.

Diffusive gradients in thin-films (DGT) sampler with a polyquaternary ammonium salt (PQAS) aqueous solution as a binding phase and a dialysis membrane as a diffusive phase (PQAS DGT) was developed for the measurement of dissolved reactive phosphorus (DRP) in water. The performance of PQAS DGT was not dependent upon pH 3-10 and ionic strength from 1 × 10(-4) to 1 mol L(-1). The effective binding capacity of PQAS DGT containing 2.0 mL of 0.050 mol L(-1) PQAS solution was estimated as 9.9 μg cm(-2). The measurement of DRP in a synthetic solution by PQAS DGT over a 48 h deployment period demonstrated high consistency with the concentration of DRP in the synthetic solution measured directly by the ammonium molybdate spectrophotometric method. Field deployments of PQAS DGT samplers allowed for accurate measurement of the DRP concentration in situ. The advantages of PQAS DGT include no requirement of the elution steps and direct concentration measurements of the binding phase.

Sampling and Characterizing Rare Earth Elements in Groundwater in Deep-Lying Fractures in Granitoids Under In Situ High-Pressure and Low-Redox Conditions

Several countries are preparing to dispose of radioactive nuclear waste deep underground in crystalline rock. This type of bedrock is commonly extensively fractured and consequently carries groundwater that serves as a medium for transporting metals and radionuclides. A group of metals of particular interest in this context is the rare earth elements (REEs), because they are analogues of actinides contained within radioactive waste and are tracers of hydrological pathways and geochemical processes. Concentrations of REEs are commonly low in these groundwaters, leading to values below detection limits of standard monitoring methods, particularly for the heavy REEs. We present a new technical set-up for monitoring REEs (and other trace metals) in groundwater in fractured crystalline rock. The technique consists of passing the fracture groundwater, commonly under high pressure and containing reduced chemical species, through a device that maintains the physicochemical character of the groundwater. Within the device, diffusive gradient in thin-film (DGT) discs are installed in triplicate. With this set-up, we studied REEs in groundwater in fractures at depths of approximately −144, −280, and −450 m in granitoids in the Aspo Hard Rock Laboratory in southern Sweden. The entire REE suite was detected (concentrations down to 0.1 ng L−1) and was differently fractionated among the groundwaters. The shallowest groundwater, composed of dilute modern Baltic Sea water, was enriched in the heavy REEs, whereas the deeper groundwaters, dominated by old saline water, were depleted in the heavy REEs. Deployment periods varying from 1 to 4 weeks delivered similar REE concentrations, indicating stability and reproducibility of the experimental set-up. The study finds that 1 week of deployment may be enough. However, if the overall setting and construction allow for longer deployment times, 2–3 weeks will be optimal in terms of reaching reliable REE concentrations well above the detection limit while maintaining the performance of the DGT samplers.

Using diffusive gradients in thin-films for in situ monitoring of dissolved phosphate emissions from freshwater aquaculture

The high concentrations of phosphorus and suspended matter in freshwater aquaculture are often an environmental concern and given the difficulties for sample preservation, an in situ monitoring tool would be most useful. The diffusive gradients in thin-films (DGT) technique can be used for on site monitoring and also has the advantage to integrate measurements over time and thus partly record ephemeral concentrations peaks. In this study, several DGT deployments were done in fisheries in different geographical areas: Québec, Canada and Lancashire, UK. The results obtained using the DGT technique were compared with standard measurements. The deployment periods varied from 24 h to 21d. The results show that the DGT technique can be used to measure reactive phosphorus in freshwater aquaculture up to 4-day deployment periods before biofilm buildup on the DGT device begins to interfere with diffusion and measurements. We obtained good reproducibility in the phosphorus determinations and moreover, this technique integrates daily and hourly variations of phosphorus and the DGT sampler is easy to use and deploy.