Brian Dimock

Chromatographic pre-concentration of Hg from dilute aqueous solutions for isotopic measurement by MC-ICP-MS

Previous studies have demonstrated both mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) of Hg isotopes in the environment and the potential for their application in biochemistry and geochemistry. However, little has been reported for Hg isotope geochemistry in natural aqueous environment due to the very low concentration (1–20 ng/L). We report here, for the first time, a new protocol for directly pre-concentrating Hg using AG 1 × 4 ion-exchange resin, which allows the measurement of Hg isotope composition in freshwater samples. The protocol is validated by testing both synthetic and natural solutions of varying concentrations, and by assessing the effect of Hg recovery and organic complexants on the reproducibility and the accuracy of measured isotopic ratios. The method results in acceptable procedural blanks and quantitative yields (101% ± 6%) in the final Hg eluates. The instrumental mass bias was corrected using modified empirical external normalization (MEEN) with Tl as internal dopant. The sensitivity of the method to the solution matrix (Hg/Tl ratio, organic matter concentration) was also evaluated. The pre-concentration and isotopic measurement protocol was applied to 16 natural water samples with Hg concentrations ranging from 0.9 ng/L to 15600 ng/L. The result showed a total variation of 2.4‰ for δ202Hg and evident MDF and MIF of Hg isotopes. Our study demonstrates that more research is required to fully understand the behavior of Hg isotopes in the aqueous environment.

A novel approach for determining total titanium from titanium dioxide nanoparticles suspended in water and biosolids by digestion with ammonium persulfate

Titanium dioxide (i.e. TiO(2)) in nano-form is a constituent of many nanomaterials that are used in sunscreens, cosmetics, industrial products and in biomedical applications. Quantification of TiO(2) nanoparticles in various matrixes is a topic of great interest for researchers studying the potential health and environmental impacts of nanoparticles. However, analysis of TiO(2) as Ti(4+) is difficult because current digestion techniques require use of strong acids that may be a health and safety risk in the laboratory. To overcome this problem, we developed a new method to digest TiO(2) nanoparticles using ammonium persulfate as a fusing reagent. The digestion technique requires short times to completion and optimally requires only 1 g of fusing reagent. The fusion method showed >95% recovery of Ti(4+) from 6 μg mL(-1) aqueous suspensions prepared from 10 μg mL(-1) suspension of different forms of TiO(2,) including anatase, rutile and mixed nanosized crystals, and amorphous particles. These recoveries were greater than open hot-plate digestion with a tri-acid solution and comparable to microwave digestion with a tri-acid solution. Cations and anions commonly found in natural waters showed no significant interferences when added to samples in amounts of 10 ng to 110 mg, which is a much broader range of these ions than expected in environmental samples. Using ICP-MS for analysis, the method detection limit (MDL) was determined to be 0.06 ng mL(-1), and the limit of quantification (LOQ) was 0.20 ng mL(-1). Analysis of samples of untreated and treated wastewater and biosolids collected from wastewater treatment plants yielded concentrations of TiO(2) of 1.8 and 1.6 ng mL(-1) for the wastewater samples, respectively, and 317.4 ng mg(-1) dry weights for the biosolids. The reactions between persulfate ions and TiO(2) were evaluated using stoichiometric methods and FTIR and XRD analysis. A formula for the fusing reaction is proposed that involves the formation of sulfate radicals.

Development of the DGT technique for Hg measurement in water: Comparison of three different types of samplers in laboratory assays

The Diffusive Gradients in Thin films (DGT) technique is an operationally defined method to determine the dissolved fraction of trace elements in water. The aim of this study was to develop this technique for the measurement of the bioavailable mercury species in natural waters. For that purpose, three types of DGT units (commercial, manufactured with agarose diffusive gel (DG) and manufactured with polyacrylamide DG) were tested under controlled conditions using an Hg(II) solution both with and without dissolved organic matter (DOM). An acid digestion method using aqua regia was optimised to efficiently digest the resin gel discs prior to analysis. A good performance was obtained for the three DGT types when deployed in a DOM-free mercury solution in the laboratory, and it was demonstrated that polyacrylamide gel can be used as diffusive layer for mercury sampling. However, when the DGT units were deployed in a mercury solution containing DOM, performance differences were observed. Furthermore, the mass of background mercury (blanks) varied among the different DGT types. In the light of the results, the devices manufactured with polyacrylamide DG seemed to be the best choice for dissolved mercury determination.

Development of pre-concentration procedure for the determination of Hg isotope ratios in seawater samples.

Hg concentrations in seawater are usually too low to allow direct (without pre-concentration and removal of salt matrix) measurement of its isotope ratios with multicollector-inductively coupled plasma mass spectrometry (MC-ICP-MS). Therefore, a new method for the pre-concentration of Hg from large volumes of seawater was developed. The final method allows for relatively fast (about 2.5Lh(-1)) and quantitative pre-concentration of Hg from seawater samples with an average Hg recovery of 98±6%. Using this newly developed method we determined Hg isotope ratios in seawater. Reference seawater samples were compared to samples potentially impacted by anthropogenic activity. The results show negative mass dependent fractionation relative to the NIST 3133 Hg standard with δ(202)Hg values in the range from -0.50‰ to -1.50‰. In addition, positive mass independent fractionation of (200)Hg was observed for samples from reference sites, while impacted sites did not show significant Δ(200)Hg values. Although the influence of the impacted sediments is limited to the seawater and particulate matter in very close proximity to the sediment, this observation may raise the possibility of using Δ(200)Hg to distinguish between samples from impacted and reference sites.

Predicting Net Mercury Methylation in Sediments Using Diffusive Gradient in Thin Films Measurements

Diffusive gradient in thin film (DGT) sediment probes for methylmercury (MMHg) were successfully deployed for up to 30 h in three mudflat sediments in San Francisco Bay for measuring labile fractions of dissolved MMHg in pore water. Our calculations show that the local DGT-induced depletion of MMHg in sediment pore waters should be fully compensated by the natural in situ MMHg production and its subsequent remobilization from the solid phase. DGT results were interpreted in terms of labile pore water concentration and provide MMHg concentration depth profiles with a centimeter resolution. Average concentrations of DGT-labile MMHg were 2.10 ± 0.29 and 1.64 ± 0.30 ng L(-1) at China Camp and Hamilton Army Airfield sediment pore waters, respectively, while the riverine location at Petaluma showed a distinct peak of 7.1 ng L(-1) near the sediment surface. Using isotope-enriched mercury species, high resolution depth profiles of MMHg net production rates ranging from 0.2 to 9.8 ng g(-1) d(-1) were obtained in parallel sediment cores sampled closely to DGT deployment sites. A positive, linear relationship between MMHg net production rates and labile MMHg concentrations acquired through DGT measurements was found and explained 79% of the variability in the data set. The latter illustrates that mercury methylation, a biogeochemical process, strongly affected the quantity of MMHg accumulated by the DGT device in the sediment and suggests that DGT measurements have the potential to predict net methylation rates.

Two Centuries of Coral Skeletons from the Northern South China Sea Record Mercury Emissions from Modern Chinese Wars

The contemporary mercury (Hg) cycle in the worlds oceans has been greatly affected by human activities. However, we are still lacking reliable, long-term, and continuous records of Hg in seawater. Here, we report for the first time on using annually banded Porites coral skeletons from the northern South China Sea (SCS) as an archive for recording changes of seawater dissolved Hg spanning the past two centuries. We developed a combustion-trapping method to preconcentrate ultratrace Hg concentrations from coral aragonitic skeletons for highly accurate total Hg measurements. Results show that Hg in the coral skeletons ranges from 0.3 to 5.1 pmol/g and is discriminated against Ca during coral skeletal calcification. Preindustrial (1798-1832) Hg levels in coral skeletons were found to be approximately 0.5 pmol/g. The highest Hg concentrations (3-5 pmol/g) were observed during the WWII period (1933-1942). Other distinct Hg maxima (∼3 pmol/g) are observed for the periods 1833-1847, 1858-1862, 1918-1927, 1978-1982, and 1988-1992, with the first four coinciding with contemporary Chinese wars. Our study suggests that the production and use of ammunitions in those wars likely account for the primary Hg emission sources in the northern SCS before 1950, and coral is potentially a robust indicator of historical, regional Hg contamination events.

Novel silica sol–gel passive sampler for mercury monitoring in aqueous systems

A novel passive sampler for mercury monitoring was prepared using organosilica sol-gel materials. It comprises a binding layer with thiol groups for mercury complexation and a porous diffusive layer through which mercury can diffuse and arrive at the binding layer. Our study demonstrated that this new sampler follows the principle of passive sampling. The mass of mercury accumulated in the binding layer depends linearly on the mercury concentration in solution, the sampling rate and the exposure time. A typical sol-gel sampler is characterized by a diffusive layer of 1.2 μm, in which mercury ions diffuse with a coefficient of D=0.09×10(-6) cm(2) s(-1), resulting in an uptake R(s) of 8.8 mL h(-1). The capacity for mercury uptake is approximately 0.64 μg cm(-2). Mercury diffusion and binding in the passive sampler are independent of the type of mercury-chloride complex, which potentially opens the door to use this device for mercury monitoring in a wide range of natural waters.

Mercury mobility and effects in the salt-marsh plant Halimione portulacoides: Uptake, transport, and toxicity and tolerance mechanisms

The plant Halimione portulacoides, an abundant species widely distributed in temperate salt-marshes, has been previously assessed as bioindicator and biomonitor of mercury contamination in these ecosystems. The present study aims to assess uptake and distribution of total mercury (THg) and methylmercury (MMHg) within H. portulacoides, potential mercury release by volatilization through leaves, and toxicity and tolerance mechanisms by investigating plant photochemical responses. Stem cuttings of H. portulacoides were collected from a salt-marsh within the Tagus estuary natural protected area, and grown under hydroponic conditions. After root development, plants were exposed to 199HgCl2 and CH3201HgCl, and sampled at specific times (0, 1, 2, 4, 24, 72, 120, 168 (7 days) and 432 h (18 days)). After exposure, roots, stems and leaves were analysed for total 199Hg (T199Hg) and MM201Hg content. Photobiology parameters, namely efficiency and photoprotection capacity, were measured in leaves. Both THg and MMHg were incorporated into the plant root system, stems and leaves, with roots showing much higher levels of both isotope enriched spikes than the other plant tissues. Presence of both mercury isotopes in the stems and leaves and high significant correlations found between roots and stems, and stems and leaves, for both THg and MMHg concentrations, indicate Hg translocation between the roots and above-ground organs. Long-term uptake in stems and leaves, leading to higher Hg content, was more influenced by temperature and radiation than short-term uptake. However, the relatively low levels of both THg and MMHg in the aerial parts of the plant, which were influenced by temperature and radiation, support the possibility of mercury release by stems and leaves, probably via stomata aperture, as a way to eliminate toxic mercury. Regarding photochemical responses, few differences between control and exposed plants were observed, indicating high tolerance of this salt marsh plant to THg and MMHg.