Bioavailability assessment of phosphorus and metals in soils and sediments: a review of diffusive gradients in thin films (DGT)

This paper provides an overview of the principle and latest development of the diffusive gradients in thin films (DGT) technology and its applications in environmental studies with a focus on bioavailability assessment of phosphorus and metals in sediments and soils. Compared with conventional methods, DGT, as a passive sampling method, has significant advantages: in situ measurement, time averaged concentrations and high spatial resolution. The in situ measurement avoids artificial influences including contamination of samples and sample 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 the biogeochemical heterogeneity of elements of interest distributed in microenvironments, such as in the rhizosphere and the vicinity of the sediment-water interface. Moreover, DGT is a dynamic technique which simultaneously considers the diffusion 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. DGT provides potential for applications in agriculture, environmental monitoring and the mining industry. However, the 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.     

Trace metal speciation during dry and wet weather flows in the Tama River, Japan, by using diffusive gradients in thin films (DGT)

The labile species of Ni, Cu, Zn, Cd, and Pb in the Tama River, an urban river in Tokyo, Japan, were measured using diffusive gradients in thin films (DGT) method under dry and wet weather conditions, and the results were compared with total dissolved concentrations in hourly samples collected in parallel. A total of 10 DGT deployments were made and 251 hourly samples were collected during 2 rounds of sampling, conducted between August and October, 2006. Two types of diffusive gradients in thin films (DGT) devices-DGT-RG for labile inorganic and DGT-APA for total (inorganic and organic) labile species-were applied throughout the samplings. The proportions of metals measured by DGT, compared with the dissolved metal concentrations (filtered using a membrane of 0.5 microm pore size), were 38 +/- 5% (RG) and 45 +/- 8% (APA) for Ni and 45 +/- 22% (RG) and 53 +/- 23% (APA) for Zn. No labile Cu was detected throughout the sampling; Cu was assumed to be in stable complexed forms. Labile Pb was detected in 3 out of 10 deployments only; the rest were lower than the detection limit. Dissolved and labile Cd concentrations were below the detection limits. Three rain events encountered during the sampling periods were evaluated. Rains brought considerably higher loads of metals in dissolved form, and DGT measurements indicated that labile metal loads also increased. Selected DGT measurements were compared with the WHAM 6 speciation model and found to be similar to the model-computed results.     

Application of DET (diffusive equilibrium in thin films) and DGT (diffusive gradients in thin films) techniques in the study of the mobility of sediment-bound metals in the outer section of Songkhla Lake, Southern Thailand

The techniques of diffusive equilibrium in thin films (DET) and diffusive gradients in thin films (DGT) were used in the outer section of Songkhla Lake, Thailand in order to obtain high-resolution profiles of total dissolved and labile trace metals in the sediment pore water and investigate benthic fluxes. Six DET probes and six DGT probes were deployed at the mouths of the Phawong, Samrong and U-Taphao canals. A close correspondence could be observed between the high-resolution profiles of Fe and As, revealing a close link between the reductive remobilization of Fe oxides and the reduction of As(V). Co and Ni DGT profiles showed a close correspondence with Mn, but a narrow mobilization zone. Reductive mobilization of Mn oxides and associated metals and sulfide precipitation control the behaviour of these metals. The DGT profiles of Cu, Zn, Cd and Pb show surface maximum, probably linked to organic matter degradation. Important benthic fluxes, especially for As, were found at the mouths of the U-Taphao and Phawong canals.     

Comparison of diffusive gradients in thin film technique with traditional methods for evaluation of zinc bioavailability in soils

The technique of diffusive gradients in thin film (DGT) has been shown to be a promising tool to assess zinc (Zn) bioavailability in soils, but there exists considerable debate on its suitability. In this study, Zn bioavailability was systematically investigated in wheat- and maize-grown soils using this technique and seven traditional methods, including soil solution concentration and six widely used single-step extraction methods (HAc, EDTA, NaAc, NH₄Ac, CaCl₂, and MgCl₂). The concentrations of Zn in the shoots and roots of these two plant species increased continuously with increasing additions of Zn to the soils, accompanied by significant decreases in shoot biomass and root biomass at Zn concentrations greater than 400 mg kg^?1 for maize and 800 mg kg^?1 for wheat. Zinc uptake and accumulation was higher in maize roots than in wheat roots. Both the concentrations of bioavailable Zn measured by DGT (C _DGT) and soil solutions (C _sol) increased linearly with increasing additions of Zn to the soils, while no strong linear relationships were observed for the extraction methods. Higher concentrations of extractable Zn, lower values of C _sol, and larger values of R (i.e., the ratio of C _DGT to C _sol) were observed in maize-grown soils compared with those of wheat-grown soils, while the values of C _DGT between the two plants were similar. These findings demonstrate that there likely exists a stronger resupply of Zn from the soil solid phases in maize-grown soils to satisfy a higher Zn uptake and accumulation in this plant. Linear correlation analyses showed that C _DGT had the highest correlation coefficients with plant Zn concentrations compared with other traditional methods, implying that the DGT technique is more sensitive and robust in reflecting Zn bioavailability in soils to plants.     

Evaluation of diffusive gradients in thin films technique (DGT) for measuring Al, Cd, Co, Cu, Mn, Ni, and Zn in Amazonian rivers

Studies concerning the lability and bioavailability of trace metals have played a prominent role in the search for contamination of water resources. This work describes the first application yet of the diffusive gradients in thin films technique (DGT) to the determination of the fraction of free plus labile metals in waters from the Amazon Basin. Due to the complexity of the use of DGT for samples with low ionic strength and high organic matter content (characteristic of Amazonian rivers), a new analytical procedure was developed. The method is based on the determinations of apparent diffusion coefficients (D_ap) in the laboratory, by performing deployments in samples collected in the corresponding sites of study. The D_ap thereby determined is then used for in situ measurements. The suitability of the proposed approach for determination of labile Al, Cd, Co, Cu, Mn, Ni, and Zn in the Amazon River and Rio Negro (English: Black River) was evaluated. Except for Co, Mn (in a deployment at Rio Negro), Ni and Zn (in a deployment at Amazon River), labile in situ measurements were lower or similar to dissolved concentrations, indicating suitability of the proposed approach.     

Monitoring of (bio)available labile metal fraction in a drinking water treatment plant by diffusive gradients in thin films

A performance study of diffusive gradients in thin films (DGT) and inductively coupled plasma optical emission spectrometry (ICP-OES) was applied for the monitoring of the labile fraction of metals Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn, in Sant Joan Despí Drinking Water Treatment Plant located in the South of Barcelona’s Metropolitan Area (Spain). The DWTP monitoring protocol was optimized by working for 1 day of deployment (24 h) with the DGT device in contact with both treated and river water matrixes. Additionally, it was demonstrated that an increase in the deployment time of 1 week did not decrease the evaluated concentrations of the studied metals. The quality parameters of the DGT device and ICP-OES determination, such as limit of quantification, accuracy expressed as relative error (%) and reproducibility expressed as relative standard deviation, were evaluated. Good results were obtained for all the metals in ultrapure water; limits of quantification ranged from 1.5 μg L^− 1 for cadmium to 28 μg L^− 1 for zinc when deployment time of 24 h was used and from 0.2 μg L^− 1 for cadmium to 4 μg L^− 1 for zinc when this time was increased by 1 week. Accuracy and precisions lower than or equal to 10% were obtained at a parametric concentration value of the metals regulated in the European Drinking Water Guidelines (98/83/EC). DGT deployment was tested in river and treated water, and good results were obtained for Cd, Ni, Co and Zn, whereas for the other metals, a continuous control of their metallic labile fractions was monitored. Therefore, DGT device allows the continuous monitoring of the labile metal species in a drinking water treatment plant.     

Preservation of sulfidic waters containing dissolved As(III)

Solutions containing variable concentrations of sulfide (0 to 31 ppm) and arsenite (0.35 to 10 ppm) were subjected to several different preservation treatments. As predicted by equilibrium thermodynamics, at near-neutral pH the experimental solutions were undersaturated with respect to orpiment (As2S3). However, upon acidification to pH 2 with HCl or HNO3, instantaneous precipitation of poorly crystalline As2S3 occurred in sulfidic solutions which resulted in the loss of dissolved arsenite. These results have implications concerning the practice of acidifying water samples containing hydrogen sulfide with HCl or HNO3 for the purpose of preserving total arsenic values. If a near-neutral water sample contains 1 ppm arsenite and as little as 0.4 ppm sulfide, loss of dissolved arsenic will occur upon acidification. An alternative three-step preservation method involving base addition, oxidation, and acidification is proposed and investigated as an appropriate technique for preserving sulfide-bearing aqueous samples for total arsenic.     

Monitoring of labile metals in turbid coastal seawater using diffusive gradients in thin-films

Diffusive gradients in thin-films (DGT) have been investigated for in situ monitoring of labile metals in north Australian coastal seawater. Field and experimental data showed that DGT devices provided adequate detection limits, accuracy and precision for monitoring of near-pristine levels of labile Mn, Co, Cu, Cd and Pb when deployed for periods of 3 days. However, Zn could not be adequately determined due to high blank levels. The ratio of DGT-labile to 0.45 microm-filtered metal levels in natural seawater ranged from 0.44-0.63 for Cu but was close to unity for Co and Cd. Elevated levels of suspended particulate matter up to 57.3 mg l(-1) did not have an adverse effect on the performance of DGT.     

Bioavailability of copper,cadmium, zinc,and lead in tropical savanna soils assessed by diffusive gradient in thin films (DGT) and ion exchange resin membranes

The technique of diffusion gradient in thin films (DGT) for assessing bioavailable metals has not been tested under field conditions. We assessed the relationships of DGT- and cation exchange resin-membrane-measured concentrations of Cd, Cu, Pb, and Zn with plant uptake of the metals under greenhouse and field conditions. In the greenhouse, the effective concentrations of Cu, Pb, and Zn by DGT correlated significantly with uptake by sorghum (Sorghum bicolor), but cation exchange resin-membrane-measured concentrations of Cd, Pb, and Zn did not correlate with sorghum uptake. In the field, the DGT-measured concentrations of Cd, Pb, and Zn were not linearly related to uptake Cd, Pb, and Zn by lettuce (Lactuca sativa) except for Cu uptake (r = 0.87, p < 0.05). Similarly, it was only the resin-membrane-extractable Pb that correlated with Pb uptake by lettuce (r = 0.77; p < 0.05). However, fitting non-linear regression models improved the plant metal uptake predictions by DGT-measured bioavailable Cd, Cu, Pb, and Zn under field conditions. In conclusion, the DGT technique was fairly predictive of bioavailability in the greenhouse, but not in the field.     

The development of a chemical 'fingerprint' to characterise dissolved organic matter in natural waters

A suite of twelve assays has been used to 'fingerprint' dissolved organic matter (DOM). The assays were applied directly to filtered natural water samples. Temperature, pH and conductivity accounted for the environmental conditions on-site. Bulk carbon characteristics were assayed by measuring UV absorbance at 200 and 240 nm, colour in grade Hazen, DOC (dissolved organic carbon), fluorescence (excitation 370 nm, emission 450 nm) and the complexation of phenol itself. Measuring hydroxybenzenes ('monophenolics'), polyhydroxybenzenes ('polyphenolics') and total phenolics with the Gibbs, Prussian Blue and Folin-Ciocalteau assays, respectively, determined the phenolics pool. The methodology was tested on six freshwater sites in North Wales chosen to provide differences in vegetation, land-use and water chemistry and sampled once during each season. A novel approach for the presentation of the data has been developed that combines all range normalised assay results for each site and each season within one polar plot, hence the term 'fingerprint'. The data was also analysed using principal component factor analysis. Assays characterised as determining the chemical properties of DOM contributed to Factor 1 and explained 59% of the variation in the data. Assays apparently determined by the water matrix, contributed to Factor 2 and explained 20% of the variation within the data. The factor scores obtained for each site showed more variation for assays relating to the chemical properties of DOM than to the surrounding water matrix. The methodology was found to detect chemical changes within DOM for each site throughout the year and different responses for different sites.     

Copper fractionation with dissolved organic matter in natural waters and wastewater--a mixed micelle mediated methodology (cloud point extraction) employing flame atomic absorption spectrometry

A cloud point extraction-preconcentration methodology for the speciation analysis of free and organically complexed metal species in natural waters is presented. The method is based on the neutralization of the electrostatic charge of the humate-metal complexes with a positively charged surfactant in a high ionic strength solution environment. The resulting complexes are conveniently solubilized in the micelles of a non-ionic surfactant medium and are thus separated from the bulk aqueous phase. Free metal species are also determined by complexation with a conventional chelating agent under mild conditions. The overall procedure is easy, rapid and allows for a high sample throughput in terms of massive analysis of many samples in the same time period. The method offers substantially low detection limits of 8.5 and 0.9 micrograms l-1 for bound and labile species respectively, with a calibration curve rectilinear in the wide range 40-150 micrograms l-1 for the humate associated and 4-40 micrograms l-1 for the free metal species. The method is free from interferences yielding recoveries in the range 97-102% for various samples of different matrixes.     

Field cryofocussing hydride generation applied to the simultaneous multi-elemental determination of alkyl-metal(loid) species in natural waters using ICP-MS detection

Two hydride generation manifold systems, utilizing flow injection and cryotrapping techniques for alkyl-metal(loid) speciation analysis in natural waters, are described in this paper. They provide shipboard capacity for simultaneous derivatization of analytes with NaBH4 and cryotrapping of the generated products in a field packed column at -196 degrees C. The first system is a large-volume hydride generator, using a reagent-injection flow technique as a flow batch type, that has been fully optimized and applied to the simultaneous detection of alkylated species in estuarine waters. The technique permits the analysis of a large volume sample (0.5-11) at a sampling rate of 3 h-1. The second is an online continuous flow hydride generator. A sampling rate of 3-12 h-1 can be achieved with samples of 0.1-0.51. In addition, shipboard operation eliminates major problems related to sample pretreatment, transport and storage. Ultra-trace multi-element determination is finally performed in the laboratory by cryogenic GC hyphenated with ICP-MS. Routine detection limits of 0.5-10 pg (as metal) for 0.51 water samples were achieved for the selected alkyl-metal(loid) species of arsenic, germanium, mercury and tin. Concentrations of various species, obtained from water samples taken from the Rhine estuary, are also presented. These species include alkylated arsenic compounds, other than methyl derivatives, that have been tentatively identified and are reported here for the first time.     

Thresholds in eutrophication of natural waters

The population density of bacterioplankton and the concentration of dissolved organic carbon combined is a useful indicator to monitor subtle variations in the amount of eutrophication. Both parameters can be measured precisely and readily by widely accepted routine techniques that require little skill. Thresholds of eutrophication can be established to maintain the Health of Natural Waters using this indicator.     

Monitoring of eutrophication by microbial uptake kinetics of dissolved organic matter in waters

The monitoring of eutrophication can be performed by measuring the turnover times of amino acids in watermasses using the Wright-Hobbie uptake kinetics approach.The substrate specificity of amino acids varies greater with turnover times than with sampling location in watermasses with a certain water type. Thus a specific substrate among the essential amino acids should be selected to use for measuring the turnover time, in order to monitor precisely the state of trophic excitation within the steady-state oscillation in a certain aquatic system. On the other hand, either singular or plural substrates among the essential amino acids can be used for measuring the turnover time for the identification of a watermass, relevant to eutrophication.     

Behaviors of dissolved antimony in the Yangtze River Estuary and its adjacent waters

Antimony is a naturally occurring and cumulatively toxic element. With increasing concern as an inorganic contaminant, research on its environmental behavior is becoming a necessity. However, very little is known about this element. To further understand its biogeochemical behaviors and roles in the ecosystem, the main species of dissolved inorganic antimony (Sb(iii) and Sb(v)) in Yangtze River Estuary and its adjacent waters were determined by hydride generation and atomic fluorescence (HG-AFS) in our study. Results show that in surface water, the concentration for Sb(iii) and Sb(v) were in the range 0.029 μg L(-1)～ 0.736 μg L(-1) and 0.121 μg L(-1)～ 2.567 μg L(-1), with averages of 0.152 μg L(-1) and 0.592 μg L(-1), respectively. While concentrations of Sb(iii) and Sb(v) in the bottom layer were much lower, ranging from 0.023 μg L(-1) to 0.116 μg L(-1) (average of 0.050 μg L(-1)) and from 0.047 μg L(-1) to 0.441 μg L(-1) (average of 0.194 μg L(-1)), respectively. Data analysis further demonstrates that the major processes controlling antimony geochemistry in the area are riverine input, atmospheric deposition, incursion of Taiwan Warm Current, and release from particulate phase. The surface-enrichment and bottom-depletion depth profile reveals it does appear as a mildly scavenged element but is less like arsenic than previously believed. Sb(v) was the predominant speciation in aquatic environment of our research, and Sb(iii) was a minor constituent of the total antimony. Regarding the adsorption-desorption process onto SPM, Sb(iii) has a higher affinity to particulate phase than Sb(v). Furthermore, the significant correlation between antimony and nutrients indicates it is an element with great biological potential, which is also an important behavior for antimony.     

Different hydrodynamic processes regulated on water quality (nutrients,dissolved oxygen,and phytoplankton biomass) in three contrasting waters of Hong Kong

The subtropical Hong Kong (HK) waters are located at the eastern side of the Pearl River Estuary. Monthly changes of water quality, including nutrients, dissolved oxygen (DO), and phytoplankton biomass (Chl-a) were routinely investigated in 2003 by the Hong Kong Environmental Protection Department in three contrasting waters of HK with different prevailing hydrodynamic processes. The western, eastern, and southern waters were mainly dominated by nutrient-replete Pearl River discharge, the nutrient-poor coastal/shelf oceanic waters, and mixtures of estuarine and coastal seawater and sewage effluent of Hong Kong, respectively. Acting in response, the water quality in these three contrasting areas showed apparently spatial–temporal variation pattern. Nutrients usually decreased along western waters to eastern waters. In the dry season, the water column was strongly mixed by monsoon winds and tidal currents, which resulted in relatively low Chl-a (<5 μg l^?1) and high bottom DO (>4 mg l^?1), suggesting that mixing enhanced the buffering capacity of eutrophication in HK waters. However, in the wet season, surface Chl-a was generally >10 μg l^?1 in southern waters in summer due to halocline and thermohaline stratification, adequate nutrients, and light availability. Although summer hypoxia (DO <2 mg l^?1) was episodically observed near sewage effluent site and in southern waters induced by vertical stratification, the eutrophication impacts in HK waters were not as severe as expected owing to P limitation and short water residence time in the wet season.     

水体中酚类化合物分光光度分析方法的研究

对国内外水体中酚类化合物现有的分光光度分析方法进行了文献综述 ,内容包括可见光分光光度法、紫外光分光光度法、荧光分光光度法和流动注射分光光度法。在总结归纳的基础上 ,提出了水体中酚类化合物分光光度分析方法的发展方向。     

Interlaboratory comparability of copper complexation capacity determination in natural waters

The results of a test of interlaboratory comparability for the determination of copper complexation capacity and copper-ligand complex formation constant are presented. Eight water samples comprising, six natural waters, a synthetic ligand solution and a blank solution were analysed by seven laboratories using their own methods of complexation titration. Given the wide variation that might have been possible, relatively good comparability was demonstrated amongst the variety of methods for determining copper complexation capacity. The complexation capacity data largely satisfied the predefined criterion of agreement to within 50%. This provides support for the use of metal speciation criteria in the regulation of copper in the environment. Data for the determination of complex formation constants were of poorer comparability, ranging between 10(7) and 10(12) for the same water.     

A diffusive sampling device for the determination of formaldehyde in air using N-methyl-4-hydrazino-7-nitrobenzofurazan (MNBDH) as reagent

A new method utilizing the diffusive sampling of formaldehyde in air has been developed. Formaldehyde is sampled with the use of a glass fiber filter impregnated with N-methyl-4-hydrazino-7-nitrobenzofurazan (MNBDH) and phosphoric acid. The formaldehyde hydrazone formed is desorbed from the filter with acetonitrile and determined by high-performance liquid chromatography (HPLC) with UV/visible detection at 474 nm. The sampling rate was determined to be 24.7 mL min-1 with a relative standard deviation of 7% for 48 experiments. The measured sampling rates were not dependent on the formaldehyde concentration (0.1-1.0 mg m-3), sampling time (15-482 min) or relative humidity (20-85%). The detection limit was 70 micrograms m-3 for a 15 min sampling period and 2 micrograms m-3 for an 8 h sampling period.     

Modeling hourly dissolved oxygen concentration (DO) using two different adaptive neuro-fuzzy inference systems (ANFIS): a comparative study

This article presents a comparison of two adaptive neuro-fuzzy inference systems (ANFIS)-based neuro-fuzzy models applied for modeling dissolved oxygen (DO) concentration. The two models are developed using experimental data collected from the bottom (USGS station no: 420615121533601) and top (USGS station no: 420615121533600) stations at Klamath River at site KRS12a nr Rock Quarry, Oregon, USA. The input variables used for the ANFIS models are water pH, temperature, specific conductance, and sensor depth. Two ANFIS-based neuro-fuzzy systems are presented. The two neuro-fuzzy systems are: (1) grid partition-based fuzzy inference system, named ANFIS_GRID, and (2) subtractive-clustering-based fuzzy inference system, named ANFIS_SUB. In both models, 60 % of the data set was randomly assigned to the training set, 20 % to the validation set, and 20 % to the test set. The ANFIS results are compared with multiple linear regression models. The system proposed in this paper shows a novelty approach with regard to the usage of ANFIS models for DO concentration modeling.