SEGH Articles

# Diffusive gradients in thin films (DGT): An emerging technique for bioavailability assessment of chemicals in the environment

08 April 2014
As a rapidly developing passive sampling method for the labile forms of chemicals in waters, sediments and soils, the diffusive gradients in thin films (DGT) technique has significant advantages over conventional methods: in situ measurement, time averaged concentrations and high spatial resolution.

The diffusive gradients in thin films (DGT) technology provides a novel approach for the in situ measurement of the labile forms of chemical elements, such as phosphorus (P), sulphur (S), arsenic (As) and metals in waters, sediments and soils. It was invented in Lancaster in 1993. The simple device uses a hydrogel binding layer impregnated with Chelex resin or other binding agents to accumulate ions. The binding layer is overlain by a diffusive layer of hydrogel and a filter. Ions have to diffuse through the filter and diffusive layer to reach the binding layer. It is the establishment of a constant concentration gradient in the diffusive layer that forms the basis for measuring chemical element concentrations in solutions quantitatively. The effect of temperature can be predicted from the known temperature dependence of the diffusion coefficient.

Compared with conventional methods, DGT has significant advantages:

• In situ measurement
• Time averaged concentrations
• High spatial resolution

The in situ measurement avoids the artificial influences including contamination of sample collection and treatment which may change the forms of chemicals.  The time averaged concentration reflects representative measurement over a period of time. The high-resolution information captures biogeochemical heterogeneity of interested elements distributed in microenvironments, such as in rhizosphere and the vicinity of the sediment-water interface. Moreover, DGT is a dynamic technique by simultaneously considering the diffusive of solutes and their kinetic resupply from the solid phases. All the advantages of DGT significantly promote the collection of “true” information of the bioavailable or labile forms of chemicals in the environment, with potential applications in agriculture, environmental monitoring and mining industry.

The fundamental theory behind DGT is Fick’s first law of diffusion. For deployment, the unit is emerged in water or inserted into sediments or in close contact with wet soils. The labile forms of chemical elements diffuse through the filter and diffusive gel, adsorbed on the binding gel, and then quantified.

The analytes that can be measured by DGT are determined by the binding agent in use. The binding agent for the first DGT was Chelex resin for the measurements of metal ions. After that, the ferrihydrite gel was used to measure phosphorus, and silver iodide was included in the gel to take up sulphide. Recently the Zr-oxide gel was developed to measure phosphorus and inorganic arsenic with high capacities. The agents are also combined to enable simultaneous measurements of multiple analytes. For example, the hydrous zirconium oxide (Zr-oxide) has been combined with silver iodide to measure both phosphorus and sulphide, and combined with Chelex to measure phosphorus and iron.

Another significant development in DGT is the 2D high resolution measurement, which provides new evidences for the micro-scale geochemical heterogeneity. The scales have generally reached sub-millimetre level using various technologies, including proton induced X-ray emissions (PIXE), computer-imaging densitometry (CID), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), and 2D slicing.

The field applications are still at the early testing stage. Further studies are needed to properly interpret the DGT measured results under complex environmental conditions, and standard procedures and guideline values based on DGT are required to pave the way for its routine applications in environmental monitoring.

Contact: Dr. Chaosheng Zhang, School of Geography and Archaeology, National University of Ireland, Galway, Ireland; Prof. Shiming Ding, Nanjing Institute of Geography and Limnology, Chinese Academy of Sciences, Nanjing, China.

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## Science in theNews

Latest on-line papers from the SEGH journal: Environmental Geochemistry and Health

• Fertilizer usage and cadmium in soils, crops and food 2018-06-23

### Abstract

Phosphate fertilizers were first implicated by Schroeder and Balassa (Science 140(3568):819–820, 1963) for increasing the Cd concentration in cultivated soils and crops. This suggestion has become a part of the accepted paradigm on soil toxicity. Consequently, stringent fertilizer control programs to monitor Cd have been launched. Attempts to link Cd toxicity and fertilizers to chronic diseases, sometimes with good evidence, but mostly on less certain data are frequent. A re-assessment of this “accepted” paradigm is timely, given the larger body of data available today. The data show that both the input and output of Cd per hectare from fertilizers are negligibly small compared to the total amount of Cd/hectare usually present in the soil itself. Calculations based on current agricultural practices are used to show that it will take centuries to double the ambient soil Cd level, even after neglecting leaching and other removal effects. The concern of long-term agriculture should be the depletion of available phosphate fertilizers, rather than the negligible contamination of the soil by trace metals from fertilizer inputs. This conclusion is confirmed by showing that the claimed correlations between fertilizer input and Cd accumulation in crops are not robust. Alternative scenarios that explain the data are presented. Thus, soil acidulation on fertilizer loading and the effect of Mg, Zn and F ions contained in fertilizers are considered using recent $$\hbox {Cd}^{2+}$$ , $$\hbox {Mg}^{2+}$$ and $$\hbox {F}^-$$ ion-association theories. The protective role of ions like Zn, Se, Fe is emphasized, and the question of Cd toxicity in the presence of other ions is considered. These help to clarify difficulties in the standard point of view. This analysis does not modify the accepted views on Cd contamination by airborne delivery, smoking, and industrial activity, or algal blooms caused by phosphates.

• Effects of conversion of mangroves into gei wai ponds on accumulation, speciation and risk of heavy metals in intertidal sediments 2018-06-23

### Abstract

Mangroves are often converted into gei wai ponds for aquaculture, but how such conversion affects the accumulation and behavior of heavy metals in sediments is not clear. The present study aims to quantify the concentration and speciation of heavy metals in sediments in different habitats, including gei wai pond, mangrove marsh dominated by Avicennia marina and bare mudflat, in a mangrove nature reserve in South China. The results showed that gei wai pond acidified the sediment and reduced its electronic conductivity and total organic carbon (TOC) when compared to A. marina marsh and mudflat. The concentrations of Cd, Cu, Zn and Pb at all sediment depths in gei wai pond were lower than the other habitats, indicating gei wai pond reduced the fertility and the ability to retain heavy metals in sediment. Gei wai pond sediment also had a lower heavy metal pollution problem according to multiple evaluation methods, including potential ecological risk coefficient, potential ecological risk index, geo-accumulation index, mean PEL quotients, pollution load index, mean ERM quotients and total toxic unit. Heavy metal speciation analysis showed that gei wai pond increased the transfer of the immobilized fraction of Cd and Cr to the mobilized one. According to the acid-volatile sulfide (AVS) and simultaneously extracted metals (SEM) analysis, the conversion of mangroves into gei wai pond reduced values of ([SEM] − [AVS])/f oc , and the role of TOC in alleviating heavy metal toxicity in sediment. This study demonstrated the conversion of mangrove marsh into gei wai pond not only reduced the ecological purification capacity on heavy metal contamination, but also enhanced the transfer of heavy metals from gei wai pond sediment to nearby habitats.

• Cytotoxicity induced by the mixture components of nickel and poly aromatic hydrocarbons 2018-06-22

### Abstract

Although particulate matter (PM) is composed of various chemicals, investigations regarding the toxicity that results from mixing the substances in PM are insufficient. In this study, the effects of low levels of three PAHs (benz[a]anthracene, benzo[a]pyrene, and dibenz[a,h]anthracene) on Ni toxicity were investigated to assess the combined effect of Ni–PAHs on the environment. We compared the difference in cell mortality and total glutathione (tGSH) reduction between single Ni and Ni–PAHs co-exposure using A549 (human alveolar carcinoma). In addition, we measured the change in Ni solubility in chloroform that was triggered by PAHs to confirm the existence of cation–π interactions between Ni and PAHs. In the single Ni exposure, the dose–response curve of cell mortality and tGSH reduction were very similar, indicating that cell death was mediated by the oxidative stress. However, 10 μM PAHs induced a depleted tGSH reduction compared to single Ni without a change in cell mortality. The solubility of Ni in chloroform was greatly enhanced by the addition of benz[a]anthracene, which demonstrates the cation–π interactions between Ni and PAHs. Ni–PAH complexes can change the toxicity mechanisms of Ni from oxidative stress to others due to the reduction of Ni2+ bioavailability and the accumulation of Ni–PAH complexes on cell membranes. The abundant PAHs contained in PM have strong potential to interact with metals, which can affect the toxicity of the metal. Therefore, the mixture toxicity and interactions between diverse metals and PAHs in PM should be investigated in the future.