Patent Application
20240100479
This patent application claims the benefit and priority of Chinese Patent Application No. 202211159896.9, filed with the China National Intellectual Property Administration on Sep. 22, 2022, the disclosure of which is incorporated by reference herein in its entirety as part of the present application.
The present disclosure relates to the technical field of Hg(II) isotope determination in the aqueous phase, and in particular describes an in-situ enrichment and analytical method for the Hg(II) isotope in the aqueous phase.
Mercury is recognized as a global pollutant of concern due to its harmful effect on the natural environment, amplified with the extent of its proliferation. Notably, mercury is known for its ease of transportation through the atmosphere and deposition into terrestrial and aquatic ecosystems. Once being deposited into the terrestrial and aquatic ecosystems, Hg is transformed by certain anaerobic microbes to the more toxic methylmercury (MeHg), which subsequently accumulates in the food chain, posing a threat to human health and the environment. The free Hg2+ and its labile Hg(II) complexes (together referred to as Hg(II)) are the most common forms of Hg in the aqueous phase as well as the major species for Hg methylation. The Hg(II) plays a crucial role in aquatic ecosystems due to its elevated activity and bioavailability. Mercury isotopes are a powerful tracing tool to help better understanding of the biogeochemical cycling of various Hg species in the aquatic ecosystems.
Currently, accurately tracing the source and transport of Hg in the aquatic ecosystems, faces significant challenges in terms of mercury isotope technology, mainly including: traditional sampling procedures are complex and cumbersome, with stringent sampling and storage requirements. This may lead to sample contamination during collection, transportation and storage. In addition, the physical and chemical properties of the sample (e.g. pH and redox conditions) are susceptible to change. These factors may cause significant uncertainty in the determination of sample concentrations and isotopic compositions at a later stage, leading to large errors in the assay results.
In the light of this, an objective of the present disclosure is to provide an in-situ enrichment and analytical method for Hg(II) isotopes in the aqueous phase. The in-situ enrichment method minimizes the potential for contamination during the transport of the water sample to be measured and provides high accuracy in the subsequent detection of Hg(II) isotopes in the aqueous phase.
To achieve the beforementioned objective of the present disclosure, the present disclosure provides the following technical solutions.
The present disclosure provides an in-situ enrichment method for Hg(II) isotopes in the aqueous phase, including the following steps:
Preferably, the time of adsorption is longer than or equal to 24 hours.
Preferably, the in-situ enrichment method further includes performing enrichment when the eluate has the mercury concentration of lower than 0.5 ng/mL; the enrichment is conducted by the first enrichment method or the second enrichment method; the first enrichment method includes: reducing the Hg(II) by adding a reducing agent to the eluent to obtain a reduction system; blowing nitrogen into the reduction system to reverse-enrich reduced Hg(0) into diluted reverse aqua regia with a volume percentage of 40%, to obtain an Hg(II)-containing eluate that meets the criteria for MC-ICP-MS analysis; where the reducing agent is a SnCl2 aqueous solution with a concentration of 0.2 g/mL; and the nitrogen is blown at a flow rate of lower than or equal to 200 mL/min for 2 h.
Preferably, the second enrichment method includes: conducting elution a plurality of the NSBA gels in the Hg(II)-adsorbed DGT device, and combining obtained eluates to gain an Hg(II)-containing eluate that meets the criteria for MC-ICP-MS analysis.
Preferably, the Hg(II)-containing eluate has an acidity of higher than or equal to 40%.
The present disclosure further provides an analytical method for the Hg(II) isotope in the aqueous phase, including the following steps:
Preferably, quality control of the water sample is conducted by MC-ICP-MS using GBW07405 and BCR-482 solid standard materials together with NIST SRM 3133 and NIST SRM 8610 mercury isotope standard solutions as external standards as well as an NIST 997 T1 standard solution as the internal standard.
The present disclosure provides an in-situ enrichment method for Hg(II) isotopes in the aqueous phase, including the following steps: (1) conducting adsorption on the water sample by a DGT device to obtain an Hg(II)-adsorbed DGT device; where an binding gel of the DGT device is an NSBA gel; and (2) conducting elution on the NSBA gel in the Hg(II)-adsorbed DGT device obtained in step (1) to acquire an Hg(II)-containing eluate with mercury concentrations of higher than or equal to 0.5 ng/mL; where the elution is conducted with an eluent of reverse aqua regia; and the NSBA gel is a polyacrylamide hydrogel film that is internally provided with an SBA-15 mesoporous silicon material double-modified by thiol and amino groups at a molar ratio of (4-6):1. In the in-situ enrichment method, users place the DGT device and the NSBA gel in the water samples to conduct in-situ adsorption of Hg(II) without using additional samplers. Therefore, the method reduces the risk of contamination and enhances accuracy in subsequent detection of the Hg(II) isotope in the aqueous phase.
The present disclosure further provides an analytical method for the Hg(II) isotope in the aqueous phase, including the following steps: (1) conducting in-situ enrichment on the water sample by the in-situ enrichment method to obtain an Hg(II)-containing eluate; analyzing the Hg(II)-containing eluate with MC-ICP-MS to obtain the measured values of δ202Hg, Δ199Hg, and Δ201Hg; and conducting correction on the measured value of δ202Hg to obtain an actual value of δ202Hg of the water to be tested; where the correction has a correction value of −0.18‰. In the analytical method, the DGT device provided with the NSBA gel is placed in the water sample to conduct in-situ Hg(II) enrichment. Compared with traditional methods of transport of water samples, the new protocol reduces the risk of sample contamination and improves detection accuracy.
The present disclosure provides an in-situ enrichment method for Hg(II) isotope analysis in the aqueous phase, including the following steps:
the elution is conducted with an eluent of reverse aqua regia; and
the NSBA gel is a polyacrylamide hydrogel film that is internally provided with an SBA-15 mesoporous silicon material double-modified by thiol and amino groups at a molar ratio of (4-6):1.
In the present disclosure, the raw materials provided herein are all preferably commercially-available products unless otherwise specified.
In the present disclosure, adsorption is conducted on the water sample by a DGT device to obtain an Hg(II)-adsorbed DGT device; where an binding gel of the DGT device is an NSBA gel.
In the present disclosure, the NSBA gel is a polyacrylamide hydrogel film that is internally provided with an SBA-15 mesoporous silicon material double-modified by thiol and amino groups at a molar ratio of (4-6):1.
In the present disclosure, a preparation method of the NSBA gel includes preferably the following steps:
(1) in a conical flask, fully dissolving a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) with 1.9 mol/L hydrochloric acid, raising the reaction temperature to 40° C., adding ethyl orthosilicate (TEOS) dropwise at 5% of the molarity of the contained silicon to P123, stirring for 60 min, and adding (3-mercaptopropyl) trimethoxysilane (MPTMS) dropwise, where TEOS and MPTMS are added dropwise at a molar ratio of x=MPTMS/((TEOS+MPTMS)), x=0.2; after stirring for 20 h, transferring the obtained mixed solution to an autoclave, aging at 100° C. for 24 h, and subjecting an obtained product to cooling, suction filtration, washing, and drying;
In the present disclosure, the adsorption is conducted for preferably longer than or equal to 24 h.
In the present disclosure, a shell, a filter membrane, and a diffusion layer of the DGT device each are purchased from Nanjing Vision Environmental Science & Technology Ltd. The filter membrane of the DGT device is preferably prepared with polyethersulfone (PES), and has a pore size of preferably 0.45 μm and a thickness of preferably 0.14 mm. The diffusion layer of the DGT device is preferably prepared by agarose gel, and has a thickness of preferably 0.8 mm. The DGT device has other structures consistent with the prior art.
In the present disclosure, elution is conducted on the NSBA gel in the Hg(II)-adsorbed DGT device to obtain an Hg(II)-containing eluate with a mercury concentration of higher than or equal to 0.5 ng/mL.
In the present disclosure, before elution, the NSBA gel in the Hg(II)-adsorbed DGT device is preferably rinsed. The rinsing is conducted with a reagent including preferably deionized water. There is no special limitation on rinsing time and frequency, as long as the impurities in the NSBA gel in the Hg(II)-adsorbed DGT device can be removed.
In the present disclosure, the elution is conducted with an eluent of reverse aqua regia. A volume of the eluent and an area of the NSBA gel have a ratio of preferably 5 mL: 3.14 cm 2. The elution is conducted via preferably vibration for preferably 8 h to 12 h.
In the present disclosure, the Hg(II)-containing eluate has an acidity of preferably higher than or equal to 40%, more preferably 40%.
In the present disclosure, the Hg(II) eluate has a mercury concentration of higher than or equal to 0.5 ng/mL. When the eluate has a mercury concentration of lower than 0.5 ng/mL, the in-situ enrichment method further includes preferably conducting enrichment; the enrichment includes preferably the first enrichment method or the second enrichment method.
In the present disclosure, the first enrichment method preferably includes: reducing the Hg(II) by adding a reducing agent to the eluent to obtain a reduction system; blowing nitrogen into the reduction system to reverse-enrich reduced Hg(0) into diluted reverse aqua regia with a volume percentage of 40%, to obtain an Hg(II)-containing eluate that meets the criteria for MC-ICP-MS analysis. The diluted reverse aqua regia with a volume percentage of 40% is a solution obtained by mixing the reverse aqua regia and water according to a volume ratio of 4:6. The reducing agent is preferably a SnCl2 aqueous solution with a concentration of 0.2 g/mL; and there is no special limitation on an amount of the reducing agent, as long as Hg(II) can be completely converted into Hg(0). The nitrogen is blown at preferably lower than or equal to 200 mL/min, more preferably 100 mL/min to 200 mL/min for preferably 2 h.
In the present disclosure, the second enrichment method preferably includes: conducting elution a plurality of the NSBA gel in the Hg(II)-adsorbed DGT device, and combining obtained eluates to gain an Hg(II)-containing eluate which meets the criteria for MC-ICP-MS analysis.
The present disclosure further provides an analytical method for Hg(II) isotopes in the aqueous phase, including the following steps:
In the present disclosure, in-situ enrichment is carried out on the water sample using the in-situ enrichment method to obtain an Hg(II)-containing eluate. The parameters of the in-situ enrichment are preferably consistent with the beforementioned technical solutions, and are not repeated here.
In the present disclosure, the Hg(II)-containing eluate is analyzed with MC-ICP-MS to obtain the measured values of δ202Hg, Δ199Hg, and Δ201Hg.
In the present disclosure, quality control of the water sample is preferably conducted with MC-ICP-MS using GBW07405 and BCR-482 solid standard materials together with NIST SRM 3133 and NIST SRM 8610 mercury isotope standard solutions as external standards as well as an NIST 997 T1 standard solution as the internal standard.
In the present disclosure, there is no special limitation on detection parameters of MC-ICP-MS, and detection parameters well known to those skilled in the art can be used.
In the present disclosure, correction is conducted on the measured value of δ202Hg to obtain an actual value of δ202Hg of the water to be tested.
In the present disclosure, the correction has a correction value of preferably −0.18‰.
In the present disclosure, the Hg-MDF/MIF value is preferably obtained through the following steps:
When mercury concentrations in the eluates at different time points do not reach the standard for isotope determination (not lower than 0.5 ng/mL) with MC-ICP-MS, the eluates at different time points can be reverse-enriched using a mercury enrichment system of cold vapor atomic fluorescence (CV-AFS); a specific method includes: putting 10 mL to 12 mL of an eluate to be enriched into a bubble bottle, and adding 5 mL of a SnCl2 aqueous solution with a concentration of 0.2 g/mL to the bubble bottle to reduce Hg(II), such that Hg(II) in the eluate to be enriched is converted into Hg(0); and blowing nitrogen at 100 mL/min to 200 mL/min into the bubble bottle for 2 h, such that reduced Hg(0) can be reverse-enriched in 5 mL of diluted reverse aqua regia with a volume percentage of 40%.
The proportion and isotopic values of mercury adsorbed to the DGT device at different temperatures are shown in Table 1.
As shown in Table 1 that at 15° C., 25° C., and 35° C., compared with the reference values of δ202Hg and Δ199Hg (˜0‰) in NIST SRM 3133 initial solution, during adsorption of mercury to DGT, a small Hg-MDF of about −0.2‰ in δ202Hg could occur during the experiments, however, it should be cautious that this value may vary due to the complex Hg speciation and matrices in natural waters. In contrast, no mass independent isotope fractionation (MIF) for odd-mass-number isotopes (˜0‰) were observed during the experiments at all temperatures, according to the consistent Δ199Hg and Δ201Hg observed in all experiments. This highlights the great potential to use DGT Δ199Hg and Δ201Hg values to monitor the MIF signature of Hg in natural waters.
The in-situ enrichment method and the analytical method for the Hg(II) isotope in the aqueous phase provided by the present disclosure are detailed below with reference to the examples, but these examples may not be understood as a limitation to the protection scope of the present disclosure.
Selection of an Eluent
As shown in
Indoor experimental verification
If mercury concentrations in the eluates at different time points did not reach the criterion for isotope determination (>0.5 ng/mL) with MC-ICP-MS, the eluates at different time points could be reverse-enriched using a mercury enrichment system of CV-AFS; a specific method included: 10 mL of an eluate to be enriched was put into a bubble bottle, and 5 mL of a SnCl2 aqueous solution with a concentration of 0.2 g/mL was added to the bubble bottle to reduce Hg(II), such that Hg(II) in the eluate to be enriched was converted into Hg(0); and nitrogen was blown at 100 mL/min to 200 mL/min into the bubble bottle for 2 h, such that reduced Hg(0) could be reverse-enriched in 5 mL of diluted reverse aqua regia with a volume percentage of 40%.
The instrumental stability of MC-ICP-MS was ensured via NIST SRM 3133 and three standard materials (internal and external standards). The specific results were shown in Table 2.
Table 2 shows that the measurement results were consistent with the reference values, indicating that during the measurement of all samples, MC-ICP-MS was relatively stable during operation.
As shown in Table 1, Hg-MDF produced a negative offset of 0.2‰ during the DGT adsorption of mercury. Based on this, it should be cautioned that Hg-MDF values may vary due to the complex Hg speciation and matrices in natural waters. In contrast, no mass independent isotope fractionation (MIF) for odd-mass-number isotopes (˜0‰) were observed during the experiments at all temperatures, according to the consistent Δ199Hg and Δ201Hg observed in all experiments. This implied that the MIF value detected via DGT sampling could reflect the real MIF signal of the natural samples, thereby further evidencing the reliability of the method.
Field Application
The NSBA-DGT devices were placed into a paddy soil solution then removed after 14 days. Surface impurities of the devices were rinsed by ultrapure water on site, and the device was subjected to elution and detection in the laboratory. The elution and detection were the same as those mentioned in Examples 1 and 2, and the results were shown in Table 3.
Table 3 shows that the combination of DGT and MC-ICP-MS could determine the mercury isotopic composition of Hg(II) in the aqueous phase of the paddy soil. As shown in Table 3, measured values of δ202Hg was −2.28‰ and −2.17‰, given that Hg-MDF can occur during the use of DGT and the extent of MDF may vary between laboratory and field conditions, we emphasize MIF signals, it can be seen that a slight mass-independent fractionation (MIF) was detected, and the measured values of Δ199Hg was 0.11‰ and 0.22‰.
The beforementioned descriptions are merely preferred implementations of the present disclosure. It should be noted that a person of ordinary skill in the art may further make several improvements and modifications without departing from the principle of the present disclosure, but such improvements and modifications should be deemed as falling within the protection scope of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202211159896.9 | Sep 2022 | CN | national |
