DGT Sampler Research Articles

Development of a Novel DGT Passive Sampler for Measuring Cs-137 In Situ in Marine Environments.

Cs-137 is the most released fission product in the marine environment. It is important to develop a robust in situ technique for its monitoring. The existing diffusive gradients in thin films (DGT) passive sampling techniques for in situ measurement of Cs+ have some limitations due to the ion competition and high pH of seawater. A new DGT sampler based on potassium zinc hexacyanoferrate (KZFCN) as a binding layer has been developed and investigated for the measurement of the time-weighted average concentration of Cs-137 in seawater. This binding layer proved a working pH range of 2-12 and an ionic strength of up to 0.75 M. Two types of diffusive gels were tested and agarose gel (AGE) was chosen for the KZFCN-DGT sampler. The measured Cs+ diffusion coefficient (1.71 × 10-5 cm2·s-1 at 25 °C) in the diffusive gel from seawater was within the expected range published in the literature. The measured concentrations of Cs-137 in seawater obtained by laboratory deployments of the KZFCN-DGT samplers for up to 4 weeks showed good precision (RSD = 13%) and accuracy (relative error = 8.5%) values. The performance test results demonstrated that the KZFCN-DGT sampler is suitable for long-term monitoring of Cs-137 in seawater due to its high capacity and resistance to ion competition and high pH.

Measurement of perfluoroalkyl substances in drinking water sources by DGT sampler with a novel fluorinated graphite binding gel

Extensive use of per- and polyfluoroalkyl substances (PFASs) has resulted in their widespread presence in natural waters. Concern for public health requires reliable measurement methods for determining their distribution and risks. Here, a sampling method based on diffusive gradients in thin films (DGT) was developed for measuring PFASs in drinking water sources. Fluorinated graphite (FG) particles were used to prepare the DGT binding gel for selective enrichment of trace PFASs in an aqueous environment. The FG-DGT method did not show sensitivity to relevant environmental parameters including pH (5.0–9.0), ionic strength (0.001–0.5 M), or DOM concentration (0–30 mg/L). The FG-DGT had enough capacity for deployment of up to four months. Six traditional and emerging PFASs including PFOS, PFOA, PFHpA, PFHxS, PFNA, and 6:2 FTSA at the ng/L level were detected in two major reservoirs serving as public drinking water sources by FG-DGT method coupled with liquid chromatography tandem mass spectrometry (LC-MS/MS). PFOA appeared at the highest observed concentrations in the drinking water sources. The research demonstrates that FG-DGT is an effective and efficient tool for monitoring PFASs in drinking water.

Development and application of diffusive gradients in thin films for in situ sampling of the organic UV filter 4-methylbenzylidene camphor (4-MBC) in waters.

4-Methylbenzylidene camphor (4-MBC), a typical organic UV filter (OUVF) in personal care products, is considered to be a potential endocrine disruptor due to its estrogenic activity and bioaccumulation. Although 4-MBC residues have been extensively identified in aquatic waters, little is known about their occurrence, levels, and potential risk in coastal waters. This study developed a reliable sampling approach, based on diffusive gradients in thin films (DGT) with XAD-2 as the binding agent, for monitoring 4-MBC in coastal waters. The diffusion coefficients of 4-MBC in freshwater and artificial seawater were 3.65 × 10-6 cm2/s and 3.83 × 10-6 cm2/s, respectively. XAD-2 binding gel showed rapid adsorption to 4-MBC. The accumulated masses of 4-MBC in XAD-2 DGT increased linearly with deployed time for 7days in freshwater and seawater, which agreed well with theoretical predictions. The sampling performance was independent of ionic strength (0.0001-0.5M), pH (4.0-8.5), and dissolved organic matter (0-20mg/L). Field deployment in the river estuary and bathing beach showed that DGT-measured 4-MBC concentrations were consistent in comparison with grab sampling. Environmental risk assessment showed that 4-MBC may pose a medium risk to aquatic organisms based on computed risk quotient (RQ) values. Sewage discharge is the main source of 4-MBC risk, while the residue in recreation beaches contributes more significantly in summer. The established DGT sampling is suitable for seasonal monitoring, source identification, and risk assessment of 4-MBC in coastal waters.

Simultaneous measurement of labile As (III) and As (V) in soils combining DGT and HPLC-ICP-MS

The speciation of arsenic (As) determines its biogeochemistry and ecotoxicity in soils. However, the approach to in situ monitor labile As (III) and As (V) in soils still requires more exploration. In this study, we developed a method for simultaneously obtaining in-situ data on labile As (III) and As (V) in soils using diffusive gradients in thin films (DGT) and high performance liquid chromatography-inductively coupled plasma mass spectrometry. The Fe2O3∙xH2O DGT sampler exhibited rapid and simultaneous accumulation of As (III) and As (V) in solutions within 90 min. The high efficiency of simultaneous elution of As (III) (~84 %) and As (V) (~97 %) was achieved using 0.8 % H3PO4 as eluent at 90 °C for 80 min. The method detection limits for As (III) and As (V) were 0.01 and 0.005 μg/L, respectively. This method was applied to reveal the labile As (III) and As (V) in soils in the water level fluctuation zones of the Three Gorges Reservoir, which is the largest reservoir in China. The concentrations of As (III) and As (V) measured by DGT varied with different sampling sites, ranging from 0.01 μg/L to 1.20 μg/L and from 0.01 μg/L to 0.26 μg/L, respectively. The labile As (III) exhibited the higher resupply rate from soil solid phase to soil solution than labile As (V). This study helps to achieve simultaneous in-situ quantification of labile As (III) and As (V) in soils, and will improve the understanding of As mobilization and ecotoxicity in soils.

Diffusive gradients in thin films (DGT): A suitable tool for metals/metalloids monitoring in continental waterbodies at the large network scale

The contribution of Diffusive Gradients in Thin films (DGT) passive sampling to continental water quality monitoring was assessed in a real measurement network (6 sampling campaigns, 17 stations). Ten metals/metalloids (Al, Zn, Ni, Cd, Cu, Pb, Cr, As, Se and Sb) were studied using the control laboratory's working conditions with grab and DGT passive sampling. The DGT field deployments were robust, with a 3% sampler loss rate and a <65% average relative deviation between duplicates. Compared to grab sampling, DGT showed a similar quantification frequency for half of the targeted elements but showed a higher frequency for the other half (e.g., Cd quantification at 20% with grab sampling vs. 97% with DGT). Similar concentration trends were established using DGT and grab sampling at most sites throughout the year. Notably, for some elements, trends were only provided by DGT sampling. A study of several DGT blanks showed that the device contamination was occasional and originated primarily from cross-contamination during the disassembly step. Considering this contamination, the operational sensitivity by DGT was at least between 1 and 5 times greater in comparison to that by grab sampling.Estimations of the economic cost revealed that measurement networks cost 2 to 3 times more when monitored by DGT compared to standard grab monitoring. However, the information obtained based on each type of sampling method is different. Grab sampling is easy to implement and can highlight high contamination peaks. The DGT concentrations are averaged over time and are relevant to chronic exposure evaluations. Considering the good performance of the DGT sampling highlighted in this study and its complementarity with grab sampling in terms of water quality assessments, a combination of these two types of sampling, which can be affordable, should improve the water quality evaluation within monitoring networks.

In Situ Catchment Scale Sampling of Emerging Contaminants Using Diffusive Gradients in Thin Films (DGT) and Traditional Grab Sampling: A Case Study of the River Thames, UK.

The in situ passive sampling technique, diffusive gradients in thin films (DGT), confronts many of the challenges associated with current sampling methods used for emerging contaminants (ECs) in aquatic systems. This study compared DGT and grab sampling for their suitability to screen and monitor ECs at the catchment scale in the River Thames system (U.K.) and explored their sources and environmental fate. The ubiquitous presence of endocrine disrupting chemicals, parabens, and their metabolites is of concern. This study is the first to report organophosphate esters (OPEs) in the study area. TEP (summer 13-160 and winter 18-46, ng/L) and TCPP (summer 242-4282 and winter 215-854, ng/L) were the main OPEs. For chemicals which were relatively stable in the rivers, DGT and grab sampling were in good agreement. For chemicals which showed high variation in water bodies, DGT provided a better integral of loadings and exposure than grab sampling. DGT was not as sensitive as grab sampling under the procedures employed here, but there are several options to improve it to give comparable/better performance. DGT samples require shorter preparation time for analysis in the laboratory than grab samples. Overall, DGT can be a powerful tool to characterize ECs throughout a large dynamic water system.

The performance of diffusive gradient in thin film probes for the long-term monitoring of trace level total mercury in water.

The potential of diffusive gradient in thin film (DGT) as a long-term monitoring tool to assess trace level mercury (Hg) in surface waters was evaluated. A piston type DGT sampler and a plate-type device that could hold 15 DGTs were designed. The device contained piston type DGT samplers with varying diffusive gel thicknesses, that is, 0.5, 0.75, and 1.0 mm, respectively. Three DGT devices were deployed in a lake for 5 weeks, and two were deployed in a stream for 3 weeks. In the lake, the total Hg (THg) mass accumulated in the DGT varied between 0.05 and 0.15 ng, which increased with an increase in deployment time and decreased with an increase in agarose diffusion gel thickness. The DGT concentration in the lake water for a 2 week period was estimated to be about 0.8-1.0 ng/L, which was close to the measured value of 1.1 (± 0.13) ng/L, using the grab sampling technique. However, the DGT estimated at 4 and 6 weeks showed a concentration of about 0.5-0.7 ng/L, which is about twice as small as that measured by grab sampling. This underestimation of the THg levels in water appear to be caused by additional thicknesses of the physical diffusive boundary layer (0.15, 0.5, 1.29 mm) and biofilm, outside the DGT filter. The predicted DGT concentration in the upper stream of the Nakdong River was estimated to be about 0.8-1.4 ng/L, which is similar to the value of 1.22 (± 0.29) ng/L measured in the field by grab sampling. The concentration of THg was estimated to be about 1.0-1.2 ng/L, which is similar to the values measured by grab sampling. The additional diffusion thickness formed outside the DGT filter was 0.018 mm and 0.093 mm at 1 and 3 weeks, respectively, which is not larger than the diffusion gel thickness (0.5-1.0 mm). This was because DGT was installed in a region where the flow velocity is high, and the thickness of the diffusion boundary layer outside the filter is negligible.

Investigating Potential Limitations of Current Diffusive Gradients in Thin Films (DGT) Samplers for Measuring Organic Chemicals

The diffusive gradients in thin films (DGT) passive sampler has emerged as a powerful tool for measuring in situ concentrations of organic contaminants in waters with appropriate spatial and temporal resolution at low cost. This study addresses the property range of compounds which can be routinely sampled with the present design of DGT device. Sorption experiments and DGT deployment with 9 model chemicals [organophosphate esters with a wide range of log KOW (0.8-9.5), molecular weight (182-435 Da)] and different functional groups showed compounds with high hydrophobicity and aromatic rings are prone to retention on membrane filters, which slows the supply of chemical to the binding resin of the sampler. The current DGT sampler (PTFE membrane filter, agarose gel diffusion layer, and HLB binding layer) is potentially reliable for measuring hydrophilic [log KOW (0.8-2.6)] and nonaromatic-ring chemicals. For compounds of higher values of KOW or with aromatic rings, knowledge of the lag phase is necessary to optimize sampling times to avoid biasing subsequent laboratory analyses. A standard procedure is used to measure lag times (from minutes to days) by exposing a series of DGT samplers in waters until linear mass accumulation in samplers is achieved. We discuss how monitoring of a wide array of organic contaminants across classes should be possible in the future with a range of validated new DGT devices, optimized for the choice of membrane filter, diffusive material, and binding resin.

Novel in situ method based on diffusive gradients in thin-films with lanthanum oxide nanoparticles for measuring As, Sb, and V and in waters

Lanthanum oxide nanoparticles (nano-La2O3) was used to develop a novel binding gel within an in situ passive sampler based on diffusive gradients in thin-films technique (NL-DGT) for measuring As(V), Sb(V), and V(V). Performance characteristics of NL-DGT were independent of pH (pH: 3.1–7.9 for As, 3.1–8.5 for V, and 3.1–6.5 for Sb) and ionic strength (0.1–500 mmol L−1 for As and V, and 0.1–200 mmol L−1 for Sb). No obvious competition effects among As, Sb, and V with different concentration ratios were found for NL-DGT measurement. Long term storage (8–188 d) of the nano-La2O3 gels in 0.01 mol L−1 NaNO3 at 4 °C did not affect their performance. During the field deployments in Yangtze and Jiuxiang River, NL-DGT measured concentrations of As and V were similar to those measured by the grab samples, while some differences were found for Sb between DGT and grab sampling because higher pH (∼8.0) in the studied rivers caused the performance deterioration of NL-DGT. Generally, the newly developed NL-DGT is suitable for monitoring As and V in freshwater from acidic to light alkaline and Sb in acidic and neutral water.

Coupling mesoporous imprinted polymer based DGT passive samplers and HPLC: A new tool for in-situ selective measurement of low concentration tetrabromobisphenol A in freshwaters

Accurate measurement of tetrabromobisphenol A (TBBPA) is very important because of its widespread environmental pollution. Diffusive gradients in thin films technique (DGT), an in-situ passive sampling method, is regarded as a reliable and robust measurement technique. A new DGT technique based on mesoporous imprinted polymer was combined with high-pressure liquid chromatography (HPLC) method for sampling, preconcentration and monitoring low concentration TBBPA in natural waters. The diffusion coefficient of TBBPA through the diffusive gel was measured by diffusion cell test and simulated using mathematical expression. The effects of different ambient conditions were tested under laboratory conditions and the performance of DGT sampler was validated in natural waters. The diffusion coefficient of TBBPA in the diffusive gel was measured as 2.18 × 10−6 cm2 s−1 and simulated as in the range 1.41–3.48 × 10−6 cm2 s−1 by Amsden model. Comparison of experimental and theoretical data, the validity of the experimental method can be verified by the mathematical model. The binding agent with mesoporous imprinted polymer showed selective affinity to TBBPA and its adsorption rate met the requirement of DGT device. The DGT method detection limit was at the level of ng L−1 for 7 days deployment. DGT sampler was suitable for application in aquatic environment with a range of pH (4.5–7.6), ionic strength (1 × 10−4 - 0.5 mol L−1), and dissolved organic matter (DOM) concentration (0–10 mg C L−1). The coupling method of DGT and HPLC was a promising technique for in situ sampling, preconcentration and monitoring low concentration TBBPA in most typical natural waters.

Evaluation of a mercapto-functionalized silica binding phase for the selective sampling of SeIV by Diffusive Gradients in Thin films

This study evaluates binding discs based on 3-mercaptopropyl-functionalized silica gel for the selective sampling of selenite (SeIV) using Diffusive Gradients in Thin films sampler (DGT). SeIV accumulation was quantitative and selective over SeVI and followed the theoretical linear accumulation with the exposure time up to 0.7 µg. The sampling was not affected by ionic strength variations down to 10−2 mol L−1 (as NaNO3) but SeIV accumulation was found to decrease significantly for pH greater than 5 and was nearly zero at pH 9. Both the limited accumulation range and the pH dependence were unexpected because they have not been reported in the literature related to the SeIV trapping by thiol-based solid phases. Our experiments showed that after SeIV was bound to thiol functional groups, a further pH-dependent reaction occurred with free thiols, resulting in the reduction of SeIV into elemental selenium (Se0) followed by its release and back-diffusion through the DGT sampler. Unfortunately, such a reversible accumulation is incompatible with the implementation of the mercapto-functionalized silica binding phase in DGT devices for SeIV selective sampling.

A cyclodextrin polymer membrane-based passive sampler for measuring triclocarban, triclosan and methyl triclosan in rivers

In recent years, extensive attention has been paid to the passive sampling technology of diffusive gradients in thin films (DGT) due to its growing application in the measurement of a widening variety of compounds. Within any DGT device, the binding phase is a key component, and seeking novel binding phases is an issue worth studying. Cyclodextrin polymer, as a green and eco-friendly material, may be a good choice for measuring organic chemicals. In this study, a novel DGT sampler with cyclodextrin polymer membrane (CDPM) as the binding phase was developed for measuring the concentrations of triclosan, triclocarban and methyl triclosan. Firstly, the type and content of cyclodextrin used in CDPM was optimized, and a series of tests showed that CDPM had good hydrophilicity, thermal stability, fast uptake rate and sufficient uptake capacity, thus CDPM was determined to be suitable for use as the binding phase of DGT sampler. Moreover, the sampling rates of this DGT sampler were not influenced by ionic strength and dissolved organic matter, making it feasible for in situ monitoring of compounds in the field. Hence, we deployed the developed DGT sampler in the Qinhuai and Jiuxiang Rivers to measure the concentrations of three compounds. We also collected water samples and processed them with the solid phase extraction (SPE) method. Results indicated that there was no significant difference between the DGT-measured and the SPE-measured concentrations for each compound, which confirmed the reliability of this DGT sampler for monitoring the concentrations of compounds in natural waters.

Development and evaluation of diffusive gradients in thin films technique for measuring antibiotics in seawater

As coastal waters in many regions of the world have been polluted by organic micro-pollutants such as antibiotics that can promote the development of resistance genes, it is of importance to monitor the levels of antibiotics in coastal waters. For this purpose, a reliable and robust sampling approach based on diffusive gradients in thin films (DGT) was developed in this study. The DGT measurement can provide a time weighted average concentration of pollutants. A binding material (resin XDA-1) with a high adsorption capacity for antibiotics, which can resist the pH and ionic strength of seawaters, was selected. The DGT sampler exhibited linear accumulation for 20 antibiotics during a 12h deployment. The antibiotic measurement by the sampler was not affected by pH in the range of 7.3 to 8.9 and ionic strength in the range of 0.5 to 0.8M. After an 8-hour in situ DGT sampling, 10 antibiotics were detected in Dalian coastal seawaters with the concentrations ranging from 2.6 to 44.8ngL−1, which was comparable to the results measured by an active sampling method. This study can be a first attempt to construct DGT sampler for determining antibiotics in seawaters.

Key role of the sorption process in alteration of metal and metalloid quantification by fouling development on DGT passive samplers

The DGT technique (diffusive gradients in thin films) is widely used for passive sampling of labile trace metals and metalloids in natural waters. Although development of fouling on the protective membranes is frequently observed, its effect on DGT sampling has been barely investigated. This study evaluates the influence of fouling on sampling of trace cationic metals Cd(II), Cu(II), Ni(II) and Pb(II) and oxyanions As(V), Cr(VI), Sb(V) and Se(VI). Fouling was developed in situ on polycarbonate membranes in four diverse natural freshwater environments and sampling alteration was assessed in controlled laboratory experiments. Accumulation of oxyanions and Ni was unaltered in the presence of fouling whereas significant alteration occurred in sampling of Cd, Cu and Pb (at pH ∼5.4). Characterization of the fouled membranes highlighted the intervention of sorption phenomenon as sampling alteration was systematically observed alongside element sorption onto fouled membrane. A preliminary flowchart for identifying potentially biased quantifications linked to fouling development during in situ DGT deployment in natural waters is proposed.

Uncertainty evaluation of the diffusive gradients in thin films technique.

Although the analytical performance of the diffusive gradients in thin films (DGT) technique is well investigated, there is no systematic analysis of the DGT measurement uncertainty and its sources. In this study we determine the uncertainties of bulk DGT measurements (not considering labile complexes) and of DGT-based chemical imaging using laser ablation - inductively coupled plasma mass spectrometry. We show that under well-controlled experimental conditions the relative combined uncertainties of bulk DGT measurements are ∼10% at a confidence interval of 95%. While several factors considerably contribute to the uncertainty of bulk DGT, the uncertainty of DGT LA-ICP-MS mainly depends on the signal variability of the ablation analysis. The combined uncertainties determined in this study support the use of DGT as a monitoring instrument. It is expected that the analytical requirements of legal frameworks, for example, the EU Drinking Water Directive, are met by DGT sampling.

Comparing dissolved reactive phosphorus measured by DGT with ferrihydrite and titanium dioxide adsorbents: Anionic interferences, adsorbent capacity and deployment time

Two adsorbents (Metsorb and ferrihydrite) used in binding layers with the diffusive gradients in a thin film technique were evaluated for the measurement of dissolved reactive phosphorous (DRP) in synthetic and natural waters. Possible interferences were investigated with Cl − (up to 1.35 mol L −1) and SO 4 2− (up to 0.056 mol L −1) having no affect on either DGT binding layer, and HCO 3 − (up to 5.7 mmol L −1) having no effect on Metsorb-DGT, over 4 days. However, HCO 3 − interfered with the ferrihydrite-DGT measurement at concentrations typical of many natural waters (≥0.7 mmol L −1) after a deployment period of 1–2 days. The capacity of the Metsorb binding phase for DGT response was ∼37,000 ng P, whereas the capacities of a low-mass (17.8 mg of adsorbent per DGT sampler) and high-mass (29.2 mg of adsorbent per DGT sampler) ferrihydrite binding phase were substantially lower (∼15,000 ng P and ∼25,000 ng P, low-mass and high-mass, respectively). Increasing the capacity of the ferrihydrite adsorbent allowed the ferrihydrite-DGT to be utilized for up to 3 days before interference by HCO 3 − was observed. Seawater deployments demonstrated that even high-capacity ferrihydrite-DGT devices underestimated the DRP concentration by 37%, whereas Metsorb-DGT measurements were accurate. The Metsorb-DGT is superior to the ferrihydrite-DGT for determining DRP over deployment times greater than 1 day and in waters with ≥0.7 mmol L −1 HCO 3 −. Based on the experience obtained from this detailed validation process, the authors propose a number of key requirements that need to be considered when developing new DGT binding layers, with testing the performance over longer deployment times being critical.

Trace Metal Measurements in Low Ionic Strength Synthetic Solutions by Diffusive Gradients in Thin Films

In view of conflicting reports regarding the performance of DGT in low ionic strength solutions (I < 1 mM), further investigations have been carried out. Minimal washing of the diffusive gel and deployment in 1.0 and 10 mM NaNO3 solutions containing Cu and Cd gave the theoretical response of 1 for [C](DGT)/[C](SOLN), where [C](DGT) is the concentration of metal measured by DGT and [C](SOLN) is the concentration of metal measured directly in the solution by an appropriate analytical method. Erroneously high values for [C](DGT)/[C](SOLN) were obtained when these same gels were deployed at I = 0.1 mM, presumably due to a net negative charge on the gel, attributable to the presence of initiation products of polymerization. However, washing the diffusive gels completely, where the storage solution pH equaled that of deionized water, gave values of approximately 0.5 for [C](DGT)/[C](SOLN) from deployments at I = 0.1 mM, consistent with the lower measured value of the diffusion coefficients at this ionic strength. These results can be explained by the presence of a net positive charge on the gel when it is exhaustively washed, which reduces the effective diffusion coefficient of metal ions by changing their concentration at the gel-solution interface (Donnan partitioning). Diffusive gel equilibration experiments showed the presence of low capacity sites capable of binding metals irrespective of ionic strength. This binding within the diffusive gel does not affect most DGT measurements, as short (4 h) deployments at concentrations of 10 ppb gave theoretical results. Incomplete washing of the resin-gel caused a 5-15% measurement error and a decrease in precision, even at ionic strengths of 10 mM. A high level of accuracy and precision (typically <5%) was maintained during all aspects of this work, even at ionic strengths of 0.1 mM, in contrast to previous results. This is attributable to three factors: (1) exhaustive washing and conditioning protocols, (2) improvements to the DGT sampling device, and (3) low and reproducible blanks due to ultraclean handling procedures. Provided effective diffusion coefficients measured at the same ionic strength are used, the established DGT theory is obeyed irrespective of ionic strength.

Performance study of diffusive gradients in thin films for 55 elements.

The technique of diffusive gradients in thin films (DGT) is a fairly new and useful tool for in situ measurements of labile metal ions in water. The applicability of DGTs was investigated by comparing independently determined or estimated diffusion coefficients with DGT effective diffusion coefficients (D(DGT)) for 55 elements. The DGTs were exposed at a controlled fluid velocity of 0.1 m s(-1) and a concentration of 1 ng mL(-1) at four pH levels between 4.7 and 6.0, and the D(DGT) values were determined from the uptake by the sampler. The measured D(DGT) values for the elements Co, Ni, Cu, Zn, Cd, Pb, Al, Mn, and Ga were close to previously published values with some deviations for Pb and Zn. The uptake of V, Cr, Fe, U, Mo, Ti, Ba, and Sr varied with pH, and there were some experimental problems that require further investigations. A novel set of D(DGT) values for the lanthanides (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Tb, Yb, Lu, Y) was established. The D(DGT) values for these were about 10-15% lower than for free ions in water and indicate that diffusion coefficients of metal ions in the agarose polyacrylamide diffusive hydrogel are 10-15% lower than in water. The high consistency of the data for the lanthanides establishes these elements as new performance test metals for the DGT sampler. The accumulation of the elements Li, Na, K, Rb, Mg, Ca, B, Tl, P, S, As, Bi, Se, Si, Sn, Sb, Te, Zr, Nb, Hf, Ta, W, Th, and Ag was low (D(DGT) lower than 10% of theoretical values). A more efficient elution procedure using concentrated nitric acid for the absorbent gel was established, with elution efficiencies between 95 and 100% for most metals. For deployment times of 24 h, detection limits from 0.001 to 1 ng mL(-1) were achieved with moderate precautions to prevent contamination.

In situ measurement of trace metals in lakewater using the dialysis and DGT techniques

The technique of diffusion gradients in thin films (DGT) is designed to measure in situ labile trace metals; in a DGT device, the metal species are trapped in a resin gel comprising a Chelex resin in its Na-form after their diffusion across a diffusion layer comprising a polyacrylamide hydrogel. We deployed DGT and dialysis samplers (peepers) in the water column of the oligotrophic and acidic Lake Tantaré, Que. Canada. Contrary to expectation, concentrations of Cd and Ni measured by DGT in lake water were consistently higher than those measured by in situ dialysis. We show that co-diffusion of other ions through the diffusion layer, not taken into account explicitly in the original DGT theory, explains our field observations. When the DGT devices are deployed in a water of low major cation concentrations ( ∑[ cations]≤2×10 −4 M ), a steep negative concentration gradient of Na + across the diffusive layer as well as small positive concentration gradients of the other cations develop. The result is an increase in the effective diffusion coefficients of cations entering the DGT sampler and a decrease in the diffusion coefficient of Na + leaving the DGT device to fulfill electroneutrality. Non-steady-state conditions during the deployment time of the DGT devices make the prediction of these effects impracticable. We suggest that DGT devices, as presently designed, are not useful for measuring trace metal species in lakes of low cation concentrations. Such lakes are numerous in northern North America and in Scandinavia. Electrical effects on the diffusion coefficients were not observed in other studies using DGT samplers deployed in surface waters with major cation concentrations higher than 2×10 −4 M.