Diffusive Gradients In Thin-films Devices Research Articles

Back Accumulation of Diffusive Gradients in Thin-Films Devices with a Stack of Resin Discs To Assess Availability of Metal Cations to Biota in Natural Waters.

Determining species, concentrations, and physicochemical parameters in natural waters is key to improve our understanding of the functioning of these ecosystems. Diffusive Gradients in Thin-films (DGT) devices with different thicknesses of the resin or of the diffusive disc can be used to collect independent information on relevant parameters. In particular, DGT devices with a stack of two resin discs offer a simple way to determine dissociation rate constants of metal complexes from the accumulation of the target metal in the back resin disc. In this work, simple approximate expressions for the determination of the dissociation rate constant are reported and applied to a model Ni nitrilotriacetic complex as well as to Zn complexes in the Mediterranean Osor stream. Once the physicochemical parameters are known, one can plot the labile fraction of the metal complexes in terms of the thickness of the diffusion domain. These plots reveal a strong dependence on the nature of complexes as well as on the characteristics of the diffusion domain, and they are of high interest as predictors of availability to biota whose uptake is limited by diffusion.

Evaluation of the diffusive gradients in thin-films (DGT) technique for measuring nitrate and ammonium in soil

Environmental context Nitrate (NO3−) and ammonium (NH4+) are the most important soil nitrogen forms for plant growth. However, conventional extraction techniques may introduce artefacts affecting the measurement of plant-available N concentrations following sampling and sample preparation processes. This is the first study of the DGT technique being used to measure NO3-N and NH4-N in a wide range of soils, compared with conventional KCl extraction, and examined different factors that contribute to the plant-availability of these ions in soils. The knowledge would help to optimise soil nitrogen management practices, increase economic benefits and reduce environmental impacts. Rationale The availability of soil nitrogen for plant uptake can be affected by numerous soil factors such as soil texture, moisture and organic matter content, temperature and microbial activity. Conventional extraction techniques may affect the measurement of plant-available N concentrations following sampling and sample preparation processes, including drying, sieving, homogenising, freezing and thawing. The diffusive gradients in thin-films (DGT) technique can overcome some limitations of the conventional extraction techniques and has been used to successfully estimate the plant-available fractions of nutrients, such as P, K, Zn, Cu and Mn in soils. Therefore, it is important to evaluate the use of DGT for measuring NO3− and NH4+ in a wide variety of soils and examine the factors that contribute to the plant-availability of these ions in soils. Methodology The experiment evaluated the ability of the DGT technique to measure NO3-N and NH4-N in soils using binding layers containing A520E anion exchange resin or Microlite® PrCH cation exchange resin, respectively. The DGT results were compared to those from conventional KCl extraction. Results The A520E- and PrCH-DGTs showed good detection limits for NO3-N (6.90 µg L−1) and NH4-N (6.23 µg L−1) and were able to measure potentially available NO3-N and NH4-N in unfertilised soils. The mass of NO3-N and NH4-N that accumulated on the DGT device increased linearly across soil concentrations ranging from 5 to 300 mg kg−1 NO3-N (depending on soil type) and 5–300 mg kg−1 NH4-N; which is equivalent to fertiliser rates of 75–450 kg ha−1 N. DGTs were used to measure potentially available NO3-N and NH4-N in ten soils with various physical and chemical properties. The DGT results were compared with conventional KCl extraction used to determine soil mineral N. DGT and KCl extraction measured values were significantly correlated with each other for NO3-N (R2 = 0.53; P-value < 0.001), but the relationship between the two measurements was weaker for NH4-N (R2 = 0.20, P-value = 0.045). Discussion The results suggest that the two methods sample different N pools in the soils, with DGT targeting the NO3-N and NH4-N that are available in soil pore water and attached to labile solid phases.

A new DGT technique based on nano-sized Mg2Al layered double hydroxides with DTPA for sampling of eight anionic and cationic metals.

In this work, a new resin gel incorporated with layered double hydroxide nanoparticles modified with diethylenetriaminepentaacetic acid is developed for application in diffusive gradients in thin-film devices (abbreviated as LDHs DGT) to monitor eight anions and cations (such as Fe, Mn, Co, Ni, Cu, Cd, Pb, and As) in natural waters and soils. The accumulated anions and cations were quantitatively recovered by one-step elution using 0.5mol·L-1 HNO3 with an optimized elution time of 30min. The performance of the LDHs DGT was independent of solution pH (5-8) and ionic strengths (5-100mmol·L-1). The capacities of the LDHs DGT for Mn(II), Fe(II), Co(II), Ni(II), Cu(II), As(V), Cd(II), and Pb(II) individually are determined to be 202.9, 363.6, 246.9, 88.8, 99.5, 75.3, 159.8, and 671.7μg·cm-2. During the field deployments in anature river, LDHs DGT measured concentrations of cations and anions were almost like those measured by the traditional sampling method (except Fe(II), Cd(II), and Co(II)). In addition, bioavailable Cd measured by LDHs DGT correlated well with Cd in rice grains (R2 = 0.55), indicating that LDHs DGT is a reliable tool for assessing the risk of Cd.

Evaluation and Application of a Novel Diffusive Gradients in Thin-Films Technique for In Situ Monitoring of Glucocorticoids in Natural Waters.

The potential environmental risks of glucocorticoids (GCs) have attracted attention in the past few decades. In this study, a novel diffusive gradients in thin-films (DGT) device and analytical technique based on the second generation of polar enhanced phase (PEP-2), PEP-2-DGT, were developed for sampling and quantifying natural and synthetic GCs in aquatic systems. The capacity of PEP-2 gels for accumulating all target compounds was >600 μg per disc, sufficient for long-term passive sampling of selected GCs, even in wastewaters. Systematic tests were carried out to verify the application of DGT in natural waters and wastewaters. The performance of PEP-2-DGT devices was independent (CDGT/Csoln was in the acceptable range of 0.9-1.1) of a wide range of environmental conditions: ionic strength (0.001-0.5 mol L-1), dissolved organic matter (0-20 mg L-1), and pH (3.06-9.02). It was tested for various diffusive layer thicknesses (0.565-2.065 mm) and different deployment times (10-168 h). Diffusion coefficients (D) of selected GCs through an agarose-based diffusive gel were determined for the first time (3.80-4.85 × 10-6 cm-2 s -1 at 25 °C). Linear correlations between D and log Kow were established for three groups of target GCs (R2 = 0.96-0.99). This could enable prediction of D values for other GCs with similar structures in the future, which will help for rapid screening and emergency monitoring. Concentrations and distribution patterns of analytes obtained by PEP-2-DGT devices in five rivers after 7- and 14-day deployments were in accordance with those measured from grab samples, with total GC concentrations ranging from 7 to 27 ng L-1 at all sampling sites, confirming the reliability and robustness of the DGT devices for monitoring GCs in natural waters. The development of the new DGT technique will help improve understanding of the behavior and fate of these compounds in the aquatic environments.

Desorption kinetics of antipsychotic drugs from sandy sediments by diffusive gradients in thin-films technique

Dynamic processes of organic contaminants in sediments can have important toxicological implications in aquatic systems. The current study used diffusive gradients in thin-films (DGT) devices in sandy sediments spiked with nine antipsychotics and in field sandy sediments. Samplers were deployed for 1 to 30 days to determine the flux of these compounds to DGT devices and the exchange rates between the porewater and sediment solid phase. The results showed a continuous removal of antipsychotics to a binding gel and induced a mobile flux from the DGT device to the adjacent sediment solution. A dynamic model, DGT-induced fluxes in soils and sediments, was used to derive rate constants of resupply of antipsychotics from solid phase to aqueous phase (response time, Tc) and distribution coefficients for labile antipsychotics. The largest labile pool was found for lamotrigine and carbamazepine in spiked sediments. Carbamazepine, clozapine, citalopram, and lamotrigine were resupplied rapidly by sediments with Tc (25–30 min). Tc values of bupropion and amitriptyline were the longest (≈5 h), which exhibited slow desorption rates in sediments. In field sediments, high resupply was found for carbamazepine and lamotrigine, which did not show higher labile pool. The Tc values were obviously higher in the filed sediments (52–171 h). Although the adsorption process is dominant for most studied antipsychotics in both spiked sediments and field sediments, the kinetic resupply of antipsychotic compounds may not be accurately estimated by laboratory-controlled incubation experiments. More studies are needed to explore the mechanisms of desorption kinetics by using in situ DGT technique in the field.

Validation and Assessment of Diffusive Gradients in Thin-Films (DGT) Technique for Measuring Nutrients in Taihu Lake Water with Algae Bloom.

DGT (diffusive gradients in thin films) technique has been developed for measuring nitrogen in freshwaters and applied to assess the bioavailability of phosphorus in soils/sediments. These two elements are the main nutrients causing algae bloom, but DGT has never been used in the field water conditions with algae bloom. In our study, a pair of DGT devices were used in comparison with grab sampling to characterize the performance of this technique to measure labile NO3-N, NH4-N, and PO4-P concentrations in algae-cultivated Taihu Lake water. The results showed that DGT measurement was highly affected by algae bloom and the environmental conditions using the current assemblies, especially for NH4-N measurement. For in situ measurement of nutrients in the real environment, an improvement to the DGT technique is required. The comprehensive assessment of the level of eutrophication needs to consider a variety of environmental factors rather than just the concentration of nutrients.

Recent nanomaterials development and application in diffusive gradients in thin-film devices

Recent nanomaterials development and application in diffusive gradients in thin-film devices

Combining diffusive gradients in thin‐films (DGT) and 31P NMR spectroscopy to determine phosphorus species in soil

AbstractThe diffusive gradients in thin‐films (DGT) technique shows in many publications a superior correlation to the amount of plant‐available phosphorus (P) in soil. However, this technique cannot give information on the plant‐available P species in soil. Therefore, we combined DGT with solution 31P nuclear magnetic resonance (NMR) spectroscopy. This was achieved by using a modified DGT device in which the diffusive layer had a larger pore size, the binding layer incorporated an adsorption material with a higher capacity, and the device had a larger exposure area. The spectroscopic investigation was undertaken after elution of the deployed DGT binding layer in a NaOH solution. Adsorption tests using solutions of known organic P compounds showed that a sufficient amount of these compounds could be adsorbed on the binding layer in order for them to be analyzed by solution 31P NMR spectroscopy. Furthermore, various intermediates of the hydrolysis of trimetaphosphate in soil could be also analyzed over time.Core Ideas We show a promising combination of DGT technique and solution 31P NMR spectroscopy. This technique combination can identify organic phosphorus species in solutions. Modified DGT device can analyze the hydrolysis of trimetaphosphate in soil.

Metal forms and dynamics in urban stormwater runoff: New insights from diffusive gradients in thin-films (DGT) measurements

Stormwater runoff typically contains significant quantities of metal contaminants that enter urban waterways over short durations and represent a potential risk to water quality. The origin of metals within the catchment and processes that occur over the storm can control the partitioning of metals between a range of different forms. Understanding the fraction of metals present in a form that is potentially bioavailable to aquatic organisms is useful for environmental risk assessment. To help provide this information, the forms and dynamics of metal contaminants in an urban system were assessed across a storm. Temporal patterns in the concentration of metals in dissolved and particulate (total suspended solids; TSS) forms were assessed from water samples, and diffusive gradients in thin-films (DGTs) were deployed to measure the DGT-labile time-integrated metal concentration. Results indicate that the concentrations of dissolved and TSS-associated metals increased during the storm, with the metals Al, Cd, Co, Cu, Pb and Zn representing the greatest concern relative to water quality guideline values (GVs). The portion of labile metal as measured by DGT devices indicated that during the storm a substantial fraction (∼98%) of metals were complexed and pose a lower risk of acute toxicity to aquatic organisms. Comparison of DGT results to GVs indicate that current GVs are likely quite conservative when assessing stormwater pollution risks with regards to metal contaminants. This study provides valuable insight into the forms and dynamics of metals in an urban system receiving stormwater inputs and assists with the development of improved approaches for the assessment of short-term, intermittent discharge events.

A new approach to improve the accuracy of DGT (Diffusive Gradients in Thin-films) measurements in monitoring wells

The Diffusive Gradients in Thin-films (DGT) technique represents an ideal tool for monitoring water quality of inorganic species in systems with a high flow such as rivers, streams, lakes and seas. However, in low-flow systems (non-turbulent waters), the influence of a diffusive boundary layer (DBL) formed on the surface of the DGT device has been observed, which can lead to erroneous measurements by DGT. Therefore, the use of DGT in wells for groundwater monitoring is still very limited until now.In this sense, the present study evaluates the applicability of the DGT technique in non-turbulent and low-flow water systems. We propose a new way to calculate the DBL with the objective to carry out a robust DGT analysis in environmental monitoring wells. For this purpose, DGT devices with different diffusive gel thicknesses were deployed in an experimental set-up simulating a groundwater monitoring well. A DBL thickness (for each element) was calculated from the slopes of the linear regressions between the DGT accumulated mass of metal and the deployment time (4, 8, 12, 24 and 48 h) for each of the two diffusive gel thicknesses. The mean DBL thickness (averaging the individual DBL thicknesses calculated from the slopes) was 0.06 cm. The concentrations of the analysed elements were corrected with this DBL with the result that the metal concentrations measured by DGT improved and were highly approximated to their actual total values in this non-complexing medium.

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.

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.

WATT progresses production of residential SOFC unit components

The analytical technique DGT (Diffusive Gradients in Thin-films) is able to gain access to a wealth of information by carefully interpreting accumulation data from passive samplers with different configurations (i.e. different thicknesses of its constituent layers). A set of DGT devices were simultaneously deployed in solutions of Ni and nitrilotriacetic acid (NTA) of different concentrations to measure the availability of Ni in these solutions. Accumulations indicate that the availability of Ni depends on both the thickness of the resin and the thickness of the diffusive gel. In both cases, the lability degree increases as the thickness increases. As the formation of successive complexes (such as Ni(NTA)2) proceeds, the availability of the metal decreases, which is quantitatively explained by reducing the formulation to a case with only one complex, but with an effective dissociation rate constant that decreases as the concentration of NTA increases. Simple analytical expressions are reported to quantify the lability degree in the different DGT configurations. These results indicate that a set of different DGT devices can characterize the availability of a cation in a natural sample with uptake processes at different spatial or time scales. Alternatively, and from a more fundamental point of view, information on speciation, mobilities and labilities of the species present in natural samples can be obtained with a set of DGT configurations.

Availability of metals to DGT devices with different configurations. The case of sequential Ni complexation.

The analytical technique DGT (Diffusive Gradients in Thin-films) is able to gain access to a wealth of information by carefully interpreting accumulation data from passive samplers with different configurations (i.e. different thicknesses of its constituent layers). A set of DGT devices were simultaneously deployed in solutions of Ni and nitrilotriacetic acid (NTA) of different concentrations to measure the availability of Ni in these solutions. Accumulations indicate that the availability of Ni depends on both the thickness of the resin and the thickness of the diffusive gel. In both cases, the lability degree increases as the thickness increases. As the formation of successive complexes (such as Ni(NTA)2) proceeds, the availability of the metal decreases, which is quantitatively explained by reducing the formulation to a case with only one complex, but with an effective dissociation rate constant that decreases as the concentration of NTA increases. Simple analytical expressions are reported to quantify the lability degree in the different DGT configurations. These results indicate that a set of different DGT devices can characterize the availability of a cation in a natural sample with uptake processes at different spatial or time scales. Alternatively, and from a more fundamental point of view, information on speciation, mobilities and labilities of the species present in natural samples can be obtained with a set of DGT configurations.

Investigating Lead Species and Bioavailability in Contaminated Soils: Coupling DGT Technique with Artificial Gastrointestinal Extraction and in Vivo Bioassay.

Although strong in vivo-in vitro correlations (IVIVCs) between relative bioavailability (RBA) and bioaccessibility of soil Pb were well reported, knowledge on the fractions of bioaccessible Pb in simulated gastrointestinal (GI) fluids that are available for absorption into the systemic circulation is limited. Here, Pb-RBA in 14 Pb-contaminated soils were assessed using an in vivo mouse bioassay and compared to Pb bioaccessibility by the gastrointestinal phase of the UBM (Unified Bioaccessibility research group of Europe (BARGE) Method) in vitro assay with and without 0.45 μm filtration of GI fluid. Results showed good IVIVC between Pb-RBA and Pb bioaccessibility without filtration ( r 2 = 0.62), while Pb bioaccessibility with filtration provided a poor correlation with Pb-RBA ( r 2 = 0.16). This suggested that besides dissolved Pb ions, Pb-complexes formed in the UBM gastrointestinal fluid might also contribute to bioavailable Pb. To ascertain this, DGT (diffusive gradients in thin-films) devices which can measure both Pb2+ ions and labile inorganic and organic Pb-complexes were introduced to the UBM fluids to measure Pb DGT-bioaccessibility, which showed strong correlation to Pb-RBA ( r 2 = 0.71). With increasing diffusive gel thickness which could enhance release of Pb ions from Pb-complexes, Pb DGT-bioaccessibility increased by 3.4-5.7 times, while inclusion of dialysis membrane within DGT devices significantly decreased Pb DGT-bioaccessibility by inhibiting diffusion of Pb complexes to binding gel. These results confirmed the contribution of Pb-complexes to Pb bioavailability, providing new insights to Pb bioavailability.

Predicting Trace Metal Exposure in Aquatic Ecosystems: Evaluating DGT as a Biomonitoring Tool

Exposure to trace metals is a leading factor associated with the development of non-communicable diseases. Aquatic ecosystems are not only effective agents of trace metal dispersion but are also at risk of contaminant enrichment. The use of sentinel organism as indicators of water quality is one method to evaluate potential human and ecological risk. An alternative or companion approach is to employ chemical techniques that mimic biotic accumulation/responses by aquatic fauna. The Diffusive Gradients-in-Thin-Films (DGT) technique has been widely used in bioavailability studies in water, soil and sediment. Many efforts have been made trying to understand the relationships between DGT labile determinations of trace elements and its biouptake by different organisms. However, the relationship between DGT labile determinations and the biological accumulation/response in aquatic animals is still not clear. The present work aims to improve the understanding of this relationship by summarizing the works using DGT devices and accumulation/response by animals in aquatic media. Several papers studying nineteen different elements in aquatic media are revised and discussed. The papers were separated and discussed in four categories: DGT and Biotic response, DGT and Bioaccumulation, DGT and Biomonitoring, and DGT and Bioturbation. DGT is expected to correlate well with the biological accumulation/responses in kinetically controlled situations. In biomonitoring studies, the use of chemical (DGT) and biological approaches gives complementary and high valuable information. The use of DGT and biological approaches should be considered in future studies about bioavailability and might improve the comprehension about uptake of trace metals by the aquatic fauna.

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.

A multiscale study of mercury transformations and dynamics at the chemocline of the Petit-Saut tropical reservoir (French Guiana)

This study investigated, on both metric and centimetric scales, mercury (Hg) transformations and dynamics within a water column chemocline of a tropical reservoir. Data collected included conventional measurement of Hg in water samples, diffusive gradients in thin-films (DGT) assessments, and thermodynamic speciation modeling in order to portray the biogeochemical processes that control elemental Hg (EM) and dissolved monomethylated Hg (MeHgD) production. The primary contribution of this study is demonstration that the DGT technique can be successfully implemented to examine labile Hg compound mobilization, and estimation of how local substratum facilitates Hg reduction and methylation reactions. DGT profiles with a resolution of 1cm revealed a fine sequence of prominent Hg reduction/oxidation reactions at the chemocline level. This is interpreted as a manifestation of both: i) kinetic effects capable of arising inside the diffusive layer of DGT devices, and ii) extremely localized production or consumption of reducible and methylable Hg. Another key result obtained at the metric scale is that EM and MeHgD production at a water column chemocline are intricately linked, as both are fueled by nutrients episodically released during the decomposition of falling epilimnetic organic particles or inhibited by dissolved organic matter and inorganic compounds continuously transported from the deeper monimolimnion. Finally, it is worth noting that the chemocline acts as an accumulation and recycling domain for falling MeHg-loaded organic particles, whereas the high primary productivity layer in the epilimnion represents the principal reactor with respect to Hg methylation and reduction.

Development and evaluation of a new diffusive gradients in thin-films technique for measuring organotin compounds in coastal sediment pore water

Organotins present a toxicological risk to biota in the aquatic environment. Understanding the behaviour of these compounds in sediment is challenging, with sophisticated analytical techniques required for their measurement. We investigated the use of silica-bound sorbents for diffusive gradients in thin-films (DGT) adsorption gels to pre-concentrate five organotins (monobutlytin (MBT), dibutyltin (DBT), tributyltin (TBT), diphenyltin (DPhT), triphenyltin (TPhT)) found frequently in coastal sediment. C8 sorbent showed optimum performance in uptake and recovery of organotins for pH and ionic strength ranges typical of coastal waters. Recoveries from adsorption gels deployed in filtered sea water were MBT = 123 ± 20%, DBT = 75 ± 12%, TBT = 81 ± 16%, DPhT = 72 ± 30%, TPhT = 58 ± 10% respectively. Devices were used to investigate DGT fluxes and pore water concentrations of organotins in coastal sediment collected from a contaminated site. DGT fluxes measured in sediment cores for the five organotins ranged between 4.3 × 10−8 and 1.6 ×10−5ngcm2s−1. The depletion of organotin species within pore waters at the interface with DGT devices was measured over a series of deployment times (2, 7, 14, 21 and 28 days) and provided estimates of the concentration of organotins in pore waters at Langstone Harbour, UK, prior to depletion by the DGT device and information on their spatial heterogeneity. The novel in situ DGT device developed can pre-concentrate organotins from pore waters in coastal sediment core samples and allows their detection at low environmental concentrations using conventional gas chromatographic/mass spectrometric instrumentation. Use of the DGT device overcomes many problems associated with the conventional pore water sampling of organotins. Our preliminary data suggests it has potential in the future to be a useful tool in investigating the environmental fate of these pollutants. The use of the C8 gel will also allow for the simultaneous sequestration of other semi- and non-polar analytes present in the pore water.

Determination of labile species of As(V), Ba, Cd, Co, Cr(III), Cu, Mn, Ni, Pb, Sr, V(V), and Zn in natural waters using diffusive gradients in thin-film (DGT) devices modified with montmorillonite.

A binding phase based on the clay mineral montmorillonite (MT) was used as a sorbent in this work, which employed diffusive gradients in thin-film (DGT) devices to determine the lability of trace elements in natural waters. Montmorillonite exhibits low cost, wide availability, ease of handling, high ion-exchange capacity, and reusability. As(V), Ba2+, Cd2+, Co2+, Cr(III), Cu2+, Mn2+, Ni2+, Pb2+, Sr2+, V(V), and Zn2+ were quantitatively sorbed by MT and eluted with 1.0molL-1 HNO3, which provided efficiency above 70% of recovery. Validation tests were performed with synthetic solutions. The recovery of known concentrations ranged from 83 to 110%. The performance of modified DGT was compared with conventional DGT devices in experiments lasting 6 and 48h. The results obtained with both DGT devices showed no significant differences with 95% confidence. DGT samplers with MT were deployed in the determination of labile forms of the elements in water samples from Iguaçu River (Paraná, Brazil). The measured masses of elements in MT for various durations showed good fit to a theoretical line, indicating that the results agreed with the principle of the DGT technique. The concentrations of labile species in the sample proceeded as follows; Sr > Cd > Ba > Cu > Cr > Mn > Zn > Pb. The results suggest that DGT devices with MT are an effective alternative for speciation analysis of a wide range of elements (cations as well as anions) in natural waters.