DGT measurement of dissolved aluminum species in waters: comparing Chelex-100 and titanium dioxide-based adsorbents

Aluminum is acutely toxic, and elevated concentrations of dissolved Al can have detrimental effects on both terrestrial and aquatic ecosystems. Robust analytical methods that can determine environmentally relevant Al fractions accurately and efficiently are required by the environmental monitoring community. A simple, robust passive sampling method, the diffusive gradients in thin films (DGT) technique, was evaluated for the measurement of dissolved Al species in freshwater and marine water using either Chelex-100 or Metsorb (a titanium dioxide-based binding agent) as the adsorbent. Mass vs time DGT deployments at pH 5.05 (Al(3+) and Al(OH)(2+) dominate) and 8.35 (Al(OH)(4)(-) dominates) demonstrated linear uptake of Al (R(2) = 0.989 and 0.988, respectively) for Metsorb. Similar deployments of Chelex-DGT showed linear uptake at pH 5.05 (R(2) = 0.994); however, at pH 8.35 the mass of Al accumulated was 40-70% lower than predicted, suggesting that Chelex-100 is not suitable for Al measurements at high pH. The Metsorb-DGT measurement was independent of pH (5.0-8.5) and ionic strength (0.001-0.7 mol L(-1) NaNO(3)), whereas the Chelex-DGT measurement was only independent of ionic strength at pH 5.0. At pH 8.4, increasing ionic strength led to considerable underestimation (up to 67%) of Al concentration. Deployments of Metsorb-DGT (up to 4 days) in synthetic freshwater (pH range 5.4-8.1) and synthetic seawater (pH 8.15) resulted in linear mass uptakes, and the concentration measured by DGT agreed well with solution concentrations. Conversely, deployment of Chelex-DGT in synthetic seawater and freshwater (pH ≥7.7 Al(OH)(4)(-) dominant species) resulted in a decrease in accumulated mass with increasing deployment time. In situ field evaluations in fresh, estuarine, and marine waters confirmed that Metsorb-DGT was more accurate than Chelex-DGT for the measurement of dissolved Al in typical environmental waters.     

Combined gel probes for the in situ determination of dissolved reactive phosphorus in porewaters and characterization of sediment reactivity

Diffusive equilibrium in thin films (DET) and diffusive gradients in thin films (DGT) were applied in situ to obtain high spatial resolution dissolved reactive phosphorus (DRP) sediment porewater profiles in two lagoons of the Gippsland Lakes (SE Australia) during summer. Although the DRP depth profiles were different in each lake, highlighting the sensitivity of DRP to the redox state of the sediment spatial DRP variations obtained from DET and DGT showed striking similarities with depth in each lake. Comparison of DRP concentrations obtained from DGT and DET allows an assessment of the reactivity of the sediment. A dynamic numerical model of DGT-induced flux in sediments (DIFS) quantified reactivity kinetics. Sediment response time (Tc) related to sedimentary phosphorus resupply resulting from DGT-induced lowering of the porewater DRP concentration was calculated. Values of Tc ranged from 4128 to 183 400 s and from 55 to 149 400 s for Lakes Victoria and Wellington, respectively. These results indicate the limited capacity of the sediment to quickly resupply DRP to the porewater, especially in surface sediment which was always characterized by the highest Tc. Adsorption and desorption rate constants were also calculated from DIFS with values ranging from 2 x 10(-3) to 2 x 10(-2) day(-1) and from 0.3 to 21 day(-1) for Lake Victoria and from 2 x 10(-4) to 0.8 day(-1) and from 0.6 to 1558 day(-1) for Lake Wellington, respectively. Diffusive fluxes estimated from the in situ DRP gradient at the sediment-water interface by DET were 558 and 1.2 micromol m(-2) day(-1) in lakes Victoria and Wellington, respectively. Despite only a single measurement, these fluxes highlight a substantial contribution of P from the sediment to the water column in summer for Lake Victoria which is likely to contribute to the recurring blooms of blue-green algae. These calculated fluxes obtained with minimal sediment disturbance and high spatial resolution were substantially different (by a factor of 6-180) from other reported values using more conventional quantitative assessments such as diffusive fluxes (from core slicing) and benthic chambers.     

Carotenoids in crabs from marine and fresh waters of India

Quantitative and qualitative distribution of carotenoids in meat and shell of major marine crab (Charybdis cruciata) and fresh water crab (Potamon potamon) from Indian waters was assessed. The total carotenoid content was low in both species of crabs analysed, highest being 11.0 μg/g in shell of marine crab. Thin-layer chromatography (TLC) and high-performance liquid chromatography (HPLC) of carotenoid extracts indicated that the marine crab contained astaxanthin and its esters as major carotenoids and zeaxanthin was major carotenoid in fresh water crab extract. Astaxanthin and its esters contributed 67.6 and 65.5 g/100 g of total carotenoids in meat and shell of marine crab. The zeaxanthin content (g/100 g) in the carotenoid extract of meat and shell of fresh water crab was 42.0 and 74.8 of total carotenoids. The carotenoid extracts from both the crabs had higher level of unsaturated fatty acids. Oleic acid (C18:1) and palmitoleic acid (C16:1) were the predominant unsaturated fatty acid in carotenoid extract from meat of marine and fresh water crab, respectively. In the carotenoid extract from shell, eicosenoic acid (C20:1) in marine crab and linolenic acid (C18:3) in fresh water crab were the major unsaturated fatty acids.     

High-resolution, two-dimensional measurement of dissolved reactive phosphorus in sediments using the diffusive gradients in thin films technique in combination with a routine procedure

Dissolved reactive phosphorus (DRP) is the most available P form in sediments and often directly controls phytoplankton blooms in aquatic systems. In this study, a novel procedure was developed for two-dimensional (2D) measurement of DRP in sediments at a spatial resolution of 0.45 mm using the diffusive gradients in thin films (DGT) technique with a revised high-capacity binding phase (Zr oxide gel). This procedure involves DGT uptake of P in sediments, 2D slicing of the binding gel on a 0.45 × 0.45-mm grid system, elution of P from each gel square with 1 M NaOH, and microcolorimetric determination of DRP in each eluted solution using 384-microwell plates. Measurements of DRP via this procedure were tested in homogeneous solutions and sediments and produced an acceptable error (<20% relative standard deviation) for the analysis once the accumulated mass of P in each gel square reached 1.2 μg cm(-2). This method was successfully applied to produce 2D images of the DRP distribution in sediments with and without the influence of tubificid worm bioturbation, revealing a much more pronounced and localized impact from tubificid worms than that found using a one-dimensional measurement of pore water DRP concentrations at 1-cm resolution.     

In situ trace metal speciation in lake surface waters using DGT,dialysis, and filtration

In situ measurements of Fe and Mn by dialysis and diffusive gradients in thin-films (DGT) in 5 lakes (pH 4.7-7.5, ionic strength 0.3-5 mmol l(-1)) and Cu and Zn in an acidic and circumneutral lake were compared to results from on site filtration. For the most acidic lake (pH 4.7) all measurements agreed, indicating an absence of colloids and negligible complexation by organic matter. There was little difference in the Mn concentrations measured by the three techniques for any lake, consistent with it being free from complexation. Zn measured by dialysis in circumneutral water was only slightly higher than DGT measurements, appropriate to only partial complexation. Substantial differences between dialysis and DGT for Cu were consistent with complexation by fulvic and humic substances, though not to the extent predicted by the speciation code WHAM. To achieve a good fit it was necessary to adjust the pK for Cu-fulvic binding from 0.8 to 1.3 and to assume that fulvic substances dominated. The presence of low molecular weight strong binding ligands would also be consistent with the data. Differences between the three measurement methods were greatest for Fe, attributable to the presence of large oxyhydroxide colloids, organic complexation and low molecular weight, reactive hydrolysis products. Fe and Mn concentrations measured by DGT on samples returned to the laboratory were much lower than in situ concentrations, illustrating the need for in situ measurements. While use of two in situ techniques provided useful information on the speciation of these natural waters, further refinements are required for unambiguous characterization of the solution. The use of DGT with a more restricted gel that excludes complexes with humic substances should provide complementary information to in situ dialysis.     

Measurement of dissolved reactive phosphorus using the diffusive gradients in thin films technique with a high-capacity binding phase

Measurement of dissolved reactive phosphorus (DRP) by the diffusive gradients in thin films (DGT) technique was investigated using a new binding phase. Half-dried amorphous zirconium oxide (with 50 ± 5% of water content) was mixed with acrylamide solution for the preparation of the new binding phase. The resulting binding gel had a high binding capacity (223 μg P cm(-2)) for phosphate. The solution of NaOH (1 M) was used for elution of phosphate from the gel, and an elution efficiency of 0.95 was obtained. A test of DGT uptake with this gel showed its dependence on temperature, and there was no influence of pH (3 to 10) and ionic strength (10 nM to 0.1 M). Its capacity for DGT response exceeded 100 μg P cm(-2), corresponding to a DRP concentration of more than 20 mg L(-1) for a 24 h deployment with a standard DGT device at 25 °C, which was at least 50 times of the Fe-oxide gel commonly used in the present DGT technique. Measurements with this high-capacity DGT technique in a laboratory microcosm of homogeneously mixed sediments gave smooth and reproducible mass-depth profiles. This technique was well demonstrated by in situ measurements in algal- and macrophyte-dominated regions of Lake Taihu. The DGT-measured concentrations of DRP were on average 20% and 40% of the DRP concentrations in pore waters, respectively, indicating a partial resupply of the sediments to the pore waters with DRP.     

Method for the in situ calibration of a passive phosphate sampler in estuarine and marine waters

Passive samplers for phosphate were calibrated in the laboratory over a range of flow velocities (0-27 cm s(-1)) and ionic strengths (0-0.62 mol kg(-1)). The observed sampling rates were between 0.006 and 0.20 L d(-1). An empirical model allowed the estimation of these sampling rates with a precision of 8.5%. Passive flow monitors (PFMs), based on gypsum dissolution rates, were calibrated for the same range of flow velocities and ionic strength. Mass loss rates of the PFMs increased with increasing ionic strength. We demonstrate that this increase is quantitatively accounted for by the increased gypsum solubility at higher ionic strengths. We provide a calculation scheme for these solubilities for an environmentally relevant range of temperatures and salinities. The results imply that co-deployed PFMs can be used for estimating the flow effect on the in situ sampling rates of the phosphate samplers, and we expect that the same may hold for other passive samplers.     

High-resolution simultaneous measurements of dissolved reactive phosphorus and dissolved sulfide: the first observation of their simultaneous release in sediments

The reassessments of environmental processes in sediments rely upon capturing the heterogeneous features of elements at a small scale and at the same location. In this study, a diffusive gradients in thin films (DGT) technique was developed for the high-resolution simultaneous measurements of dissolved reactive phosphorus (DRP) and dissolved sulfide. A new binding gel was used in this DGT technique, which was prepared by incorporating AgI particles into the zirconium oxide binding gel previously used in the DGT measurement of DRP. The concentrations of the DRP and sulfide loaded into the binding gel were determined by a routine procedure and a computer-imaging densitometry (CID) technique, respectively. The performance of this DGT technique was tested under laboratory conditions and applied to in situ measurements in sediments of a shallow lake. Simultaneous release of DRP and dissolved sulfide was observed in a sulfide microniche with a diameter of ～3 mm and in locally aggregated zones with a length over 1 cm, which was attributed to the simultaneous reductions of Fe(III) and sulfate and the associated release of Fe-bound P in the zones of the reactive organic matter in sediments. The good performance of this technique implies that there is a great potential for the development of new DGT techniques capable of simultaneous measurements of more analytes.     

Direct hydrodynamic radius measurement on dissolved organic matter in natural waters using diffusion NMR

Dissolved organic matter from natural waters is a complex mixture of various chemical components, which play vital roles in many environmental processes such as the global carbon cycle and the fate of many key anthropogenic pollutants. Despite its environmental significance, dissolved organic matter in natural form has never been studied using nuclear magnetic resonance based hydrodynamic radius measurements due to its extremely low concentration (e.g., a few mg/L) in natural waters. In this study, NMR-based hydrodynamic radius measurements were performed directly on unconcentrated pond, river, and sea waters. The key chemical components of the dissolved organic matters from different sources were identified as carbohydrates, carboxyl-rich alicyclic molecules, and aliphatic molecules. By using the Stokes-Einstein-Sutherland equation, the average hydrodynamic radii of the three key components were calculated.     

A protocol to assess the enzymatic release of dissolved organic phosphorus species in waters under environmentally relevant conditions

A protocol to assess the potential release of dissolved reactive phosphorus (DRP) by enzymatic hydrolysis of dissolved organic phosphorus (DOP) in waters (sediment porewater and sewage liquors in this study) under environmental conditions is presented. This protocol enables the quantification of different classes of DOP compounds using a variety of phosphatase enzymes, i.e., alkaline phosphatase, phosphodiesterase, and phytase. All experiments were carried out within the pH range of most natural waters, i.e., at neutral (pH 7) or slightly alkaline pH (pH 9). Tri-sodium citrate and sodium dodecyl sulfate (SDS) were used in the assays to prevent interferences due to adsorption processes in the presence of multivalent metallic cations and to minimize protein binding. Applying this protocol revealed that labile phosphate monoesters always represented the largest fraction of enzymatically hydrolyzed P in sewage liquors and sediment porewater. Total enzymatically hydrolyzable P (EHP) represented only 16% of the TDP in the sediment porewater but up to 43% in sewage liquors. Because most of the enzymes used in this study are likely to exist in aquatic ecosystems, the EHP fraction might represent a source of potentially bioavailable P of similar magnitude to DRP.     

In situ measurement of polychlorinated biphenyls in the waters of San Diego Bay,California

Sediments of San Diego Bay (SDB) are known to contain elevated levels of polychlorinated biphenyls (PCBs). While numerous efforts have been made to monitor the spatial or temporal trends of contamination in SDB, no studies have been directed toward measurements of water column contamination. We measured PCB concentrations in the water column of SDB with an in situ sampling system. Except for one sample collected near the bay mouth, all other samples contained higher PCB concentrations than the 30-day average discharge limit established by the California Ocean Plan. The highest concentrations of water column PCBs occurred in the Central Bay, consistent with the previous findings that sediments in the Central Bay contained higher PCB levels than those in the North and South Bays. Based on the water volume of 2.2 x 10(8) cm3 at a lower water level, it was estimated that approximately 1,000 g of PCBs is transported out of SDB via tidal exchange annually. This indicates that water column transport driven by tidal exchange is a viable mechanism reducing PCB contamination within SDB.     

Factors affecting the presence of dissolved glutathione in estuarine waters

We investigated factors influencing the presence of the thiol glutathione (GSH) in estuarine waters. Our study addressed thiol phase-association, the biological release from algal cultures, and the role of copper in both thiol release and preservation. Our measurements in three diverse estuaries in the continental United States (San Diego Bay, Cape Fear Estuary, and Norfolk Estuary) show that dissolved GSH, present at sub-nanomolar levels, is preferentially partitioned into the ultra-filtrate fraction (<1 kDa) in comparison with dissolved organic carbon (DOC). Concentrations of GSH generally increased with increases in total copper (Cu)levels, although large variability was observed among estuaries. In 30-h exposure experiments, release of dissolved GSH from the diatom Thalassiosira weissflogii into organic ligand-free experimental media was a strong function of added Cu concentration. The released GSH increased from about 0.02 to 0.27 fmol/cell as Cu was increased from the background level (0.5 nM) to 310 nM in the modified Aquil media. However, excretion of GSH was lower (up to 0.13 fmol/cell) when cells were grown in surface waters of San Diego Bay, despite much higher total Cu concentrations. Experiments conducted in-situ in San Diego Bay water indicated that high concentrations of added Cu destabilized GSH, while both Mn(II) and natural colloids promoted GSH stability. In contrast, laboratory experiments in synthetic media indicated that moderate levels of added Cu enhanced GSH stability.     

Interpretation of in situ speciation measurements of inorganic and organically complexed trace metals in freshwater by DGT

The dynamic speciation technique, diffusive gradients in thin-films (DGT), has been used in freshwater to determine simultaneously, from a single set of in situ measurements, (1) the equilibrium distribution of metal ions between simple inorganic complexes and larger organic complexes and (2) information on the rates of dissociation of these complexes. DGT devices with different diffusion layer thicknesses (0.3, 0.54, 1.34, and 2.14 mm) were used to estimate the in situ dissociation kinetics. Information on the species distribution was obtained by using two types of gel, which allow relatively free (polyacrylamide, APA) and more retarded (restricted, RES) diffusion of the metal complexes. The full theoretical basis of the technique is developed and applied to in situ measurements of Mn, Fe, Co, Ni, Cu, Cd, and Pb in a pristine river (Wyre, U.K.), with high DOC(15mg L(-1)), assuming that organic complexes are dominated by fulvic acid. These first DGT measurements that do not rely on assumptions about complex lability or the distribution of species, are compared to total dissolved measurements, previously reported speciation calculations and measurements using alternative speciation techniques. Examination of calculation consistency suggests that the effective mean diffusion coefficients of metal complexes with organic matter under in situ conditions may be larger than those measured in the laboratory using extracted fulvic acid.     

MEMS needle-type sensor array for in situ measurements of dissolved oxygen and redox potential

Microelectrodes are among the most accurate and reliable monitoring devices for measuring the dynamics of biofilm processes. This paper describes a novel needle-type microelectrode array (MEA) for simultaneous in situ measurements of dissolved oxygen (DO) and oxidation reduction potential (ORP) fabricated using microelectromechanical systems (MEMS) technologies. The MEA exhibits fast response times for both DO and ORP measurements and shows a substantial increase in DO sensitivity. To demonstrate the versatility of the new sensor, it was applied to the measurement of DO and ORP microprofiles in a multispecies biofilm. This work demonstrates that the MEA is able to monitor local concentration changes with a high spatial resolution and provide the versatility of the microelectrode technique needed for biofilm studies as well as the capability for repetitive measurements. In addition, the use of MEMS technologies and batch fabrication approaches enables integration, high consistency, high yields, and mass production. With further development, it may be possible to add additional sensors to the MEA (e.g., pH, phosphate) and integrate them with a reference electrode.     

Rationale for control of anthropogenic nitrogen and phosphorus to reduce eutrophication of inland waters

Concentrations of phosphorus and nitrogen in surface waters are being regulated in the United States and European Union. Human activity has raised the concentrations of these nutrients, leading to eutrophication of inland waters, which causes nuisance growth of algae and other aquatic plants. Control of phosphorus often has had the highest priority because of its presumed leading role in limiting development of aquatic plant biomass. Experimental evidence shows, however, that nitrogen is equally likely to limit growth of algae and aquatic plants in inland waters, and that additions of both nutrients cause substantially more algal growth than either added alone. A dual control strategy for N and P will reduce transport of anthropogenic nitrogen through drainage networks to aquatic ecosystems that may be nitrogen limited. Control of total phosphorus in effluents is feasible and is increasingly being required by regulations. The control strategy for nitrogen in effluents is more difficult, but could be made more feasible by recognition that a substantial portion of dissolved organic nitrogen is not bioavailable; regulation should focus on bioavailable N (nitrate, ammonium, and some dissolved organic nitrogen) rather than total N. Regulation of both N and P also is essential for nonpoint sources.     

Biogenic phosphate minerals in manure: implications for phosphorus loss to surface waters

Phosphorus (P) is present in waterways throughout the United States at concentrations that impair water quality. Agriculture, particularly livestock production, has been identified as a major cause of this impairment Excess manure P applied to croplands has increased P losses in runoff, leading to surface water eutrophication. We conducted a long-term (36-week) incubation with poultry and dairy manures applied to a silt loam soil to elucidate mechanisms controlling manure P loss to water. Manures were applied to supply the same total P rate to soils with different antecedent plant-available P concentrations (soil test P). There was a strong synergistic effect between dairy manure and soil test P on water extractable P, while soil test P did not affect P loss from poultry manure-amended soils. Using scanning electron microscopy and energy dispersive X-ray spectroscopy, we found that poultry manure contained sparingly soluble calcium and magnesium phosphate minerals that controlled soil solution P concentrations, while dairy manure did not These minerals resemble other biogenic phosphate minerals. Our findings refute current assumptions that all manure P behaves similarly in soils and that organic forms control manure-soil P loss to water.     

Determination of microgramme quantities of dissolved sulphate in surface waters,soils and plants

A rapid and simple method is described for determining sulphate in surface waters and water extracts of soils by precipitating it as lead sulphate in 40% ethanol and measuring the residual lead in solution by means of an atomic absorption spectrophotometer. Sulphate may be determined in concentrations as low as 1 ppm in the solutions. This method can also be used to determine sulphur in plant material after it has been converted to dissolved sulphate by combustion in an oxygen-filled flask.