Aim Cysteine proteases are closely associated with many human and non-human pathological processes and are potential targets for metal ions especially Hg^2＋ and the related species. In the present work, on the basis ...Aim Cysteine proteases are closely associated with many human and non-human pathological processes and are potential targets for metal ions especially Hg^2＋ and the related species. In the present work, on the basis of to the general study on the effects of some metal ions on the activity of papain, a well-known representative of cysteine protease family, the inhibitory effects of Hg^2＋ and polysulfide complexes were studied. Results All the metal ions tested （Hg^2＋, Cu^2＋, Ag^＋, Au^3＋, Zn^2＋, Cd^2＋, Fe^3＋, Mn^2＋, Pb^2＋, Yb^3＋） inhibit the activity of papain anda good correlation between the inhibitory potency and softness-and-hardness was observed. Among the metals, Hg^2＋ was shown to be a potent inhibitor of papain with a Kiof 2 × 10^-7 mol·L^-1 among. Excessive amounts of glutathione and cysteine could reactivate the enzyme activity of papain deactivated by Hg^2＋. These evidences supported that Hg^2＋ might bind to the catalytic site of papain. Interestingly, Hg （Ⅱ） polysulfide complexes were for the first time found to inhibit papain with a Ki of 7 × 10^-6 mol·L^-1, whose potency is close to a well known mercury compound, thimerosal （Ki=2.7 × 10^-6）. In addition, Hg （Ⅱ） polysulfide complexes exhibit good permeability （ 1.9 × 10-5 cm· s^-1） to caco-2 monolayer. Conclusion These results suggested that mercury polysulfide complexes might be potential bioactive species in the interaction with cysteine proteases and other- SH-content proteins, providing a new clue to understand the mechanism of the toxicological and pharmacological actions of cinnabar and other insoluble mercury compounds.展开更多
Experiments were carried out to study the transformation of mercury in soils. Results showed that Hg 2+ was immediately converted into other forms once it entered into soils. Bentonite, humus or CaCO 3 accelera...Experiments were carried out to study the transformation of mercury in soils. Results showed that Hg 2+ was immediately converted into other forms once it entered into soils. Bentonite, humus or CaCO 3 accelerated the transformation of Hg 2+ by various mechanisms. Bentonite could convert Hg 2+ into residual form eventually, and application of CaCO 3 enhanced the formation of inorganic Hg. Humus competed strongly with clay minerals for binding Hg 2+ , thus increase of soil humus content led to increased formation of organically bound Hg.展开更多
The effects of mercury ions on gold cyanidation were studied. The results show that under low cyanide concentration, gold cyanide process is controlled by CN- transfer, while at higher cyanide concentration, there for...The effects of mercury ions on gold cyanidation were studied. The results show that under low cyanide concentration, gold cyanide process is controlled by CN- transfer, while at higher cyanide concentration, there forms passivation on gold surface. Therefore, chemical oxidation of gold in cyanide solution of higher concentration is controlled by surface reaction. Small quantity of additions of mercury ions bring about great increases in anodic gold dissolution rate, decreases the passivation and reduces the equilibrium activated energy. In addition, they also markedly change the effect pattern of cyanide concentration. Mercury ions show positive effects on cathodic reduction of oxygen and raise the rate of electrochemical step of the cathodic reduction of oxygen. Addition of a certain amount of hydrogen peroxide is confirmed to be an effective way for intensification of cathodic process on gold electrode. Active potential range and current peak on anodic dissolution are enlarged when being co-intensified with Hg^2＋ and hydrogen peroxide. Co-intensifying effect may be obtained and gold from gold concentrates. gold leaching rate is considerably increased on cyanide leaching of展开更多
Mercury sulfide (HgS) crystals with different morphologies and particle sizes, were obtained via a simple microwave reaction by a new precursor complex, [bis ((2-suphanylphenyl)imino]methylphenol) Hg(II)] ([Hg(C13H11N...Mercury sulfide (HgS) crystals with different morphologies and particle sizes, were obtained via a simple microwave reaction by a new precursor complex, [bis ((2-suphanylphenyl)imino]methylphenol) Hg(II)] ([Hg(C13H11NSO)2]2+). The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet–visible (UV?Vis) spectroscopy. Mercury sulfide nanostructures with different sizes were prepared. The effects of precursor concentration, type of solvent, microwave time, and power on the particle size and morphology were investigated. The results show that the type of solvent and microwave power play key roles in the final size of HgS. Ethylene glycol is the best solvent for the synthesis of very fine particles of HgS, and the best power for the preparation of HgS nanoparticles with uniform size distribution is 900 W. The band gap for HgS nanoparticles calculated by UV–Vis spectrum was 3.2 eV which had about 1.2 eV blue shift in comparison with the band gap of 2 eV for bulk sample.展开更多
S A new cyclomercurated ferrocenylketimine containing pyridyl ring ([HgCl(5- C5H3C(CH3)=N-3-C5H4N)Fe(5-C5H5)]紺H2Cl2, Mr = 581.66) was synthesized and its molecular structure has been confirmed by IR, elemental analys...S A new cyclomercurated ferrocenylketimine containing pyridyl ring ([HgCl(5- C5H3C(CH3)=N-3-C5H4N)Fe(5-C5H5)]紺H2Cl2, Mr = 581.66) was synthesized and its molecular structure has been confirmed by IR, elemental analysis, 1H-NMR and X-ray crystal structure analysis. It is of monoclinic system, space group P21/c with a = 9.213(2), b = 17.479(4), c = 11.510(2) ? b = 100.32(3)o, V = 1823.7(6) 3, Z = 4, C17.5H16Cl2FeHgN2, Dc = 2.119 g/cm3, m = 9.497 mm-1, F(000) = 1100, R = 0.0436 and wR = 0.0987. The independent reflections are 3527, of which 3153 with I ≥ 2s(I) were observed. The compound contains a five-membered metallocycle. The mercury atom is bonded with the 2-position of substituted cyclopentadienyl ring (Cp), and coordinated weakly to the N atom of imino group. The pyridyl ring is almost perpendicular to the substituted Cp which is nearly coplanar with the metallocycle. The Hg(1)C(1) and Hg(1)Cl(1) bond lengths are 2.050(8) and 2.321(2) ? respectively.展开更多
We studied the effects of mercury (Hg2+) on antioxidant and digestive enzyme activities in terms of LC50 value and on hepatopancreas histostructures of juvenile Chinese mitten crabs Eriocheir sinensis in 40-day exposu...We studied the effects of mercury (Hg2+) on antioxidant and digestive enzyme activities in terms of LC50 value and on hepatopancreas histostructures of juvenile Chinese mitten crabs Eriocheir sinensis in 40-day exposure to various concentrations of Hg2+ (0, 0.01, 0.05, 0.10, 0.20, and 0.30 mg/L). The results show that the activities of superoxide dismutase (SOD), glutathione peroxidase (GPX) and catalase (CAT) significantly increased in the concentrations of 0.01 and 0.05 mg/L, while that of enzyme decreased in 0.10, 0.20 and 0.30 mg/L treatments. Meanwhile, Hg2+ disrupted the histostructures of the hepatopancreas, causing decreases in activities of pepsin, tryptase, amylase, and cellulose, which are synthesized in the hepatopancreas. Moreover, as the Hg2+ concentration increased, the survival rate of the crabs decreased, worst at 56.57% in 0.30 mg/L. Therefore, although crabs are able to tolerate low levels of mercury pollution, high levels lead to cellular injury and tissue damage in hepatopancreas, which then loses some of its vital physiological functions such as absorption, storage, and secretion.展开更多
A grass (Italian rye grass) experiment with complete design of three factors (Hg, grass and exposure) andtwo levels (with and without the factor tested) was carried out in Goteborg, Sweden from May to September,1995, ...A grass (Italian rye grass) experiment with complete design of three factors (Hg, grass and exposure) andtwo levels (with and without the factor tested) was carried out in Goteborg, Sweden from May to September,1995, toward understanding the effect of mercury deposition on plant Hg conteot and its distribution. It hasbeen foulld that besides the two general pathways of Hg absorption, i.e. root uptake and foliar absorption,mercury deposition can also significantly increase Hg content and total load in grass plant. Such effectsseem to be condned only within the above-ground parts of grass plant. Estimate has been made to makeclear of the contributions of different pathways to Hg content and total Hg load in the upper part of grass.Results showed that the coDtribution of Hg deposition accounted for 27%-32% of Hg content in the above-ground parts of grass plant without adding Hg to the soil, decreasing with the increase of soil and/or air Hgconcentrations. The increment of Hg load in the upper part of grass plant caused by Hg deposition duringan interval of two weeks varied between O.o1~O.o7 pg pot-1, contributing to 17%~48% of the total Hg loadin grass plant exposed.展开更多
^99Sr concentrations, resulting from the Chernobyl NPP accident, were determined in the salt lakes of the Crimea （Lakes Kiyatskoe, Kirleutskoe, Kizil-Yar, Bakalskoe and Donuzlav）, together with the redistribution be...^99Sr concentrations, resulting from the Chernobyl NPP accident, were determined in the salt lakes of the Crimea （Lakes Kiyatskoe, Kirleutskoe, Kizil-Yar, Bakalskoe and Donuzlav）, together with the redistribution between the components of the ecosystems. The content of mercury in the waters of the studied reservoirs was also established. Vertical distributions of natural radionuclide activities （^238U, ^232Th, ^226Ra, ^210pb, ^40K） and anthropogenic ^137Cs concentrations （as radiotracers） were determined in the bottom sediments of the Koyashskoe salt lake （located in the south-eastern Crimea） to evaluate the long- term dynamics and biogeochemical processes. Radiochemical and chemical analysis was undertaken and radiotracer and statistical methods were applied to the analytical data. The highest concentrations of ^99Sr in the water of Lake Kiyatskoe （350.5 and 98.0 Bq/m^3） and Lake Kirleutskoe （121.3 Bq/m^3） were due to the discharge of the Dnieper water from the North-Crimean Canal. The high content of mercury in Lake Kiyatskoe （363.2 ng/L） and in seawater near Lake Kizil-Yar （364 ng/L） exceeded the maximum permissible concentration （3.5 times the maximum）. Natural radionuclides provide the main contribution to the total radioactivity （artificial and natural combined） in the bottom sediments of Lake Koyashskoe. The significant concentration of ^210pb in the upper layer of bottom sediments of the lake indicates an active inflow of its parent radionuclide-gaseous ^222Rn from the lower layers of the bottom sediment. The average sedimentation rates in Lake Koyashskoe, determined using ^210pb and ^137Cs data, were 0.117 and 0.109 cm per year, respectively.展开更多
As a global pollutant process, the reduction of mercury （Hg） is especially important. One pathway is through an abiotic reduction with humic acids （HAs）, which is controlled by different factors, including initial...As a global pollutant process, the reduction of mercury （Hg） is especially important. One pathway is through an abiotic reduction with humic acids （HAs）, which is controlled by different factors, including initial Hg and HA concentrations, pH, temperature and light. In this study, three humic acids were selected to illustrate the Hg2＋ abiotic reduction mechanisms by HAs, and to identify the key limiting factors for reduction rates and amounts. In addition, the initial status of the HAs as a solid or in an aqueous solution were also compared, to help explain why HAs show different dominant characteristics （e.g. complexation or reduction） in the reaction process with Hg. Results indicated that HAs were able to reduce Hg abiotically. Higher initial Hg, higher HA concentrations and either high （8.1） or low （3.6） solution pH decreased the HA reduction capacity. In addition, Hg~ production rates increased with increasing temperature, and the same trend was observed with light exposure. Humic acids added as an aqueous solution resulted in significantly greater HgO production than addition as a bulk solid. Finally, the Hg reduction rate and capacity varied significantly （P 〈 0.05） with HAs from different sources. These findings helped to explain why HAs showed different dominant characteristics （e.g. complexation or reduction） in the reaction process with of Hg2＋ reduction, which indicated that humic substances in sink or a source for Hg. Hg, and evidentially demonstrated the existence of a possible pathway natural environments, especially in water bodies, could act either as a展开更多
In this paper, we report a highly sensitive chemiluminescence(CL) sensor for Hg2+ ions based on thymine-Hg2+-thymine(T-Hg2+-T) coordination chemistry. We designed a thymine rich oligonucleotide as a capture probe and ...In this paper, we report a highly sensitive chemiluminescence(CL) sensor for Hg2+ ions based on thymine-Hg2+-thymine(T-Hg2+-T) coordination chemistry. We designed a thymine rich oligonucleotide as a capture probe and a signal probe that includes two functional domains: a horseradish peroxidase-mimicking DNAzyme domain for the generation of CL, and a recognition domain. Graphene oxide(GO) was introduced to adsorb the signal probe via π-π interaction, which brought the DNAzyme domain and GO into close proximity and quenches CL. In the presence of Hg2+ ions, the coordination of Hg2+ with the capture probe yielded a hairpin complex, triggers cascaded strand displacement reactions and Exonuclease III-assisted signal amplifications. As a result, accumulated amounts of DNAzyme were generated and released from GO, leading to an enhanced CL signal. This strategy combines enzyme-based signal amplification and GO as a background reducer, leads to a limit of detection(LOD) of 2 nmol/L. This simple detection system provides a label-free yet sensitive approach for detection of Hg2+ ions.展开更多
Biogeochemical cycling of mercury in the young Three Gorges Reservoir （TGR）, China, is strongly considered. Although methylmercury （MMHg） photodegradation （PD） is an important process involved in mercury cycling...Biogeochemical cycling of mercury in the young Three Gorges Reservoir （TGR）, China, is strongly considered. Although methylmercury （MMHg） photodegradation （PD） is an important process involved in mercury cycling in this zone, little is known about this process. In situ incubation experiments were therefore performed to quantify the effect of different wave- length radiations and environmental factors on the PD process of MMHg in the water bodies of TGR. It was found that the ef- fect of solar radiation on MMHg PD was highly dependent on wavelength and water depth. All PD-rate constants resulting from each wavelength range decreased rapidly with water depth. For surface water, UV-A radiation （320-400 nm） was the key driver, accounting for 49%-62% of MMHg PD. For the entire water column, both photosynthetically active radiation （PAR, 400-700 nm） and UV-A were responsible for MMHg PD. MMHg PD fluxes peaked in summer （7.5-18 ng m-2 d-1）, followed by spring （3.3-8.0 ng m-2 d-1）, autumn （1.0-2.7 ng m-2 d-1）, and winter （0.060-0.15 ng m-2 d-1）. The annual fluxes of MMHg PD were estimated to be 1.1-2.8 μg m-2 at. Filtering the reservoir water and amending it with chemicals （i.e., CV, NO C, and dissolved organic matter （DOM）） showed significant effects on MMHg PD rate constants. Stepwise regression analysis showed that intensity of solar radiation, suspended particulate matter （SPM）, DOM, CI-, and NO3- were involved in the PD process. Path analysis clarified the relationship between MMHg PD rate constants and environmental variables, as well as the comparative strength of direct and indirect relationships among variables. The results are of great importance for understanding MMHg cycling characteristics in TGR and also facilitate the understanding of the underlying process, MMHg PD, in natural waters.展开更多
文摘Aim Cysteine proteases are closely associated with many human and non-human pathological processes and are potential targets for metal ions especially Hg^2＋ and the related species. In the present work, on the basis of to the general study on the effects of some metal ions on the activity of papain, a well-known representative of cysteine protease family, the inhibitory effects of Hg^2＋ and polysulfide complexes were studied. Results All the metal ions tested （Hg^2＋, Cu^2＋, Ag^＋, Au^3＋, Zn^2＋, Cd^2＋, Fe^3＋, Mn^2＋, Pb^2＋, Yb^3＋） inhibit the activity of papain anda good correlation between the inhibitory potency and softness-and-hardness was observed. Among the metals, Hg^2＋ was shown to be a potent inhibitor of papain with a Kiof 2 × 10^-7 mol·L^-1 among. Excessive amounts of glutathione and cysteine could reactivate the enzyme activity of papain deactivated by Hg^2＋. These evidences supported that Hg^2＋ might bind to the catalytic site of papain. Interestingly, Hg （Ⅱ） polysulfide complexes were for the first time found to inhibit papain with a Ki of 7 × 10^-6 mol·L^-1, whose potency is close to a well known mercury compound, thimerosal （Ki=2.7 × 10^-6）. In addition, Hg （Ⅱ） polysulfide complexes exhibit good permeability （ 1.9 × 10-5 cm· s^-1） to caco-2 monolayer. Conclusion These results suggested that mercury polysulfide complexes might be potential bioactive species in the interaction with cysteine proteases and other- SH-content proteins, providing a new clue to understand the mechanism of the toxicological and pharmacological actions of cinnabar and other insoluble mercury compounds.
文摘Experiments were carried out to study the transformation of mercury in soils. Results showed that Hg 2+ was immediately converted into other forms once it entered into soils. Bentonite, humus or CaCO 3 accelerated the transformation of Hg 2+ by various mechanisms. Bentonite could convert Hg 2+ into residual form eventually, and application of CaCO 3 enhanced the formation of inorganic Hg. Humus competed strongly with clay minerals for binding Hg 2+ , thus increase of soil humus content led to increased formation of organically bound Hg.
基金Project(50725416) supported by the National Science Fund for Distinguished Young Scholars,China
文摘The effects of mercury ions on gold cyanidation were studied. The results show that under low cyanide concentration, gold cyanide process is controlled by CN- transfer, while at higher cyanide concentration, there forms passivation on gold surface. Therefore, chemical oxidation of gold in cyanide solution of higher concentration is controlled by surface reaction. Small quantity of additions of mercury ions bring about great increases in anodic gold dissolution rate, decreases the passivation and reduces the equilibrium activated energy. In addition, they also markedly change the effect pattern of cyanide concentration. Mercury ions show positive effects on cathodic reduction of oxygen and raise the rate of electrochemical step of the cathodic reduction of oxygen. Addition of a certain amount of hydrogen peroxide is confirmed to be an effective way for intensification of cathodic process on gold electrode. Active potential range and current peak on anodic dissolution are enlarged when being co-intensified with Hg^2＋ and hydrogen peroxide. Co-intensifying effect may be obtained and gold from gold concentrates. gold leaching rate is considerably increased on cyanide leaching of
基金council of University of Kashan for providing financial support to undertake this work by Grant No. 159271/368
文摘Mercury sulfide (HgS) crystals with different morphologies and particle sizes, were obtained via a simple microwave reaction by a new precursor complex, [bis ((2-suphanylphenyl)imino]methylphenol) Hg(II)] ([Hg(C13H11NSO)2]2+). The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet–visible (UV?Vis) spectroscopy. Mercury sulfide nanostructures with different sizes were prepared. The effects of precursor concentration, type of solvent, microwave time, and power on the particle size and morphology were investigated. The results show that the type of solvent and microwave power play key roles in the final size of HgS. Ethylene glycol is the best solvent for the synthesis of very fine particles of HgS, and the best power for the preparation of HgS nanoparticles with uniform size distribution is 900 W. The band gap for HgS nanoparticles calculated by UV–Vis spectrum was 3.2 eV which had about 1.2 eV blue shift in comparison with the band gap of 2 eV for bulk sample.
基金This work was supported by NNSFC (No. 20072034) and NSF of Henan province
文摘S A new cyclomercurated ferrocenylketimine containing pyridyl ring ([HgCl(5- C5H3C(CH3)=N-3-C5H4N)Fe(5-C5H5)]紺H2Cl2, Mr = 581.66) was synthesized and its molecular structure has been confirmed by IR, elemental analysis, 1H-NMR and X-ray crystal structure analysis. It is of monoclinic system, space group P21/c with a = 9.213(2), b = 17.479(4), c = 11.510(2) ? b = 100.32(3)o, V = 1823.7(6) 3, Z = 4, C17.5H16Cl2FeHgN2, Dc = 2.119 g/cm3, m = 9.497 mm-1, F(000) = 1100, R = 0.0436 and wR = 0.0987. The independent reflections are 3527, of which 3153 with I ≥ 2s(I) were observed. The compound contains a five-membered metallocycle. The mercury atom is bonded with the 2-position of substituted cyclopentadienyl ring (Cp), and coordinated weakly to the N atom of imino group. The pyridyl ring is almost perpendicular to the substituted Cp which is nearly coplanar with the metallocycle. The Hg(1)C(1) and Hg(1)Cl(1) bond lengths are 2.050(8) and 2.321(2) ? respectively.
基金Supported by the National Basic Research Program of China (973 Program) (No. 2007CB407306)Basic Scientific Research Operation Cost of State-level Public Welfare Scientific Research Institute of Chinese Research Academy of Environmental Sciences (No. 2007KYYW08)
文摘We studied the effects of mercury (Hg2+) on antioxidant and digestive enzyme activities in terms of LC50 value and on hepatopancreas histostructures of juvenile Chinese mitten crabs Eriocheir sinensis in 40-day exposure to various concentrations of Hg2+ (0, 0.01, 0.05, 0.10, 0.20, and 0.30 mg/L). The results show that the activities of superoxide dismutase (SOD), glutathione peroxidase (GPX) and catalase (CAT) significantly increased in the concentrations of 0.01 and 0.05 mg/L, while that of enzyme decreased in 0.10, 0.20 and 0.30 mg/L treatments. Meanwhile, Hg2+ disrupted the histostructures of the hepatopancreas, causing decreases in activities of pepsin, tryptase, amylase, and cellulose, which are synthesized in the hepatopancreas. Moreover, as the Hg2+ concentration increased, the survival rate of the crabs decreased, worst at 56.57% in 0.30 mg/L. Therefore, although crabs are able to tolerate low levels of mercury pollution, high levels lead to cellular injury and tissue damage in hepatopancreas, which then loses some of its vital physiological functions such as absorption, storage, and secretion.
文摘A grass (Italian rye grass) experiment with complete design of three factors (Hg, grass and exposure) andtwo levels (with and without the factor tested) was carried out in Goteborg, Sweden from May to September,1995, toward understanding the effect of mercury deposition on plant Hg conteot and its distribution. It hasbeen foulld that besides the two general pathways of Hg absorption, i.e. root uptake and foliar absorption,mercury deposition can also significantly increase Hg content and total load in grass plant. Such effectsseem to be condned only within the above-ground parts of grass plant. Estimate has been made to makeclear of the contributions of different pathways to Hg content and total Hg load in the upper part of grass.Results showed that the coDtribution of Hg deposition accounted for 27%-32% of Hg content in the above-ground parts of grass plant without adding Hg to the soil, decreasing with the increase of soil and/or air Hgconcentrations. The increment of Hg load in the upper part of grass plant caused by Hg deposition duringan interval of two weeks varied between O.o1~O.o7 pg pot-1, contributing to 17%~48% of the total Hg loadin grass plant exposed.
文摘^99Sr concentrations, resulting from the Chernobyl NPP accident, were determined in the salt lakes of the Crimea （Lakes Kiyatskoe, Kirleutskoe, Kizil-Yar, Bakalskoe and Donuzlav）, together with the redistribution between the components of the ecosystems. The content of mercury in the waters of the studied reservoirs was also established. Vertical distributions of natural radionuclide activities （^238U, ^232Th, ^226Ra, ^210pb, ^40K） and anthropogenic ^137Cs concentrations （as radiotracers） were determined in the bottom sediments of the Koyashskoe salt lake （located in the south-eastern Crimea） to evaluate the long- term dynamics and biogeochemical processes. Radiochemical and chemical analysis was undertaken and radiotracer and statistical methods were applied to the analytical data. The highest concentrations of ^99Sr in the water of Lake Kiyatskoe （350.5 and 98.0 Bq/m^3） and Lake Kirleutskoe （121.3 Bq/m^3） were due to the discharge of the Dnieper water from the North-Crimean Canal. The high content of mercury in Lake Kiyatskoe （363.2 ng/L） and in seawater near Lake Kizil-Yar （364 ng/L） exceeded the maximum permissible concentration （3.5 times the maximum）. Natural radionuclides provide the main contribution to the total radioactivity （artificial and natural combined） in the bottom sediments of Lake Koyashskoe. The significant concentration of ^210pb in the upper layer of bottom sediments of the lake indicates an active inflow of its parent radionuclide-gaseous ^222Rn from the lower layers of the bottom sediment. The average sedimentation rates in Lake Koyashskoe, determined using ^210pb and ^137Cs data, were 0.117 and 0.109 cm per year, respectively.
基金Supported by the National Natural Science Foundation of China(No.40971147/D010503)the China Postdoctoral Science Foundation(No.2013M542238)+1 种基金the Fundamental Research Funds for The Central Universities,China(No.XDJK2013C151)the Ph.D.Initiation Fund of Southwest University,China(No.SWU112098)
文摘As a global pollutant process, the reduction of mercury （Hg） is especially important. One pathway is through an abiotic reduction with humic acids （HAs）, which is controlled by different factors, including initial Hg and HA concentrations, pH, temperature and light. In this study, three humic acids were selected to illustrate the Hg2＋ abiotic reduction mechanisms by HAs, and to identify the key limiting factors for reduction rates and amounts. In addition, the initial status of the HAs as a solid or in an aqueous solution were also compared, to help explain why HAs show different dominant characteristics （e.g. complexation or reduction） in the reaction process with Hg. Results indicated that HAs were able to reduce Hg abiotically. Higher initial Hg, higher HA concentrations and either high （8.1） or low （3.6） solution pH decreased the HA reduction capacity. In addition, Hg~ production rates increased with increasing temperature, and the same trend was observed with light exposure. Humic acids added as an aqueous solution resulted in significantly greater HgO production than addition as a bulk solid. Finally, the Hg reduction rate and capacity varied significantly （P 〈 0.05） with HAs from different sources. These findings helped to explain why HAs showed different dominant characteristics （e.g. complexation or reduction） in the reaction process with of Hg2＋ reduction, which indicated that humic substances in sink or a source for Hg. Hg, and evidentially demonstrated the existence of a possible pathway natural environments, especially in water bodies, could act either as a
基金supported by the National Natural Science Foundation of China(21222508,21375073)the Shanghai Municipal Commission for Science and Technology(13QH1402300)+1 种基金the State Ethnic Affairs Commission(10ZY02)the 111 Project of Minzu University(B08044)
文摘In this paper, we report a highly sensitive chemiluminescence(CL) sensor for Hg2+ ions based on thymine-Hg2+-thymine(T-Hg2+-T) coordination chemistry. We designed a thymine rich oligonucleotide as a capture probe and a signal probe that includes two functional domains: a horseradish peroxidase-mimicking DNAzyme domain for the generation of CL, and a recognition domain. Graphene oxide(GO) was introduced to adsorb the signal probe via π-π interaction, which brought the DNAzyme domain and GO into close proximity and quenches CL. In the presence of Hg2+ ions, the coordination of Hg2+ with the capture probe yielded a hairpin complex, triggers cascaded strand displacement reactions and Exonuclease III-assisted signal amplifications. As a result, accumulated amounts of DNAzyme were generated and released from GO, leading to an enhanced CL signal. This strategy combines enzyme-based signal amplification and GO as a background reducer, leads to a limit of detection(LOD) of 2 nmol/L. This simple detection system provides a label-free yet sensitive approach for detection of Hg2+ ions.
基金financially supported by the National Basic Research Program of China(2013CB430004)the National Natural Science Foundation of China(41373113 and 41173116)
文摘Biogeochemical cycling of mercury in the young Three Gorges Reservoir （TGR）, China, is strongly considered. Although methylmercury （MMHg） photodegradation （PD） is an important process involved in mercury cycling in this zone, little is known about this process. In situ incubation experiments were therefore performed to quantify the effect of different wave- length radiations and environmental factors on the PD process of MMHg in the water bodies of TGR. It was found that the ef- fect of solar radiation on MMHg PD was highly dependent on wavelength and water depth. All PD-rate constants resulting from each wavelength range decreased rapidly with water depth. For surface water, UV-A radiation （320-400 nm） was the key driver, accounting for 49%-62% of MMHg PD. For the entire water column, both photosynthetically active radiation （PAR, 400-700 nm） and UV-A were responsible for MMHg PD. MMHg PD fluxes peaked in summer （7.5-18 ng m-2 d-1）, followed by spring （3.3-8.0 ng m-2 d-1）, autumn （1.0-2.7 ng m-2 d-1）, and winter （0.060-0.15 ng m-2 d-1）. The annual fluxes of MMHg PD were estimated to be 1.1-2.8 μg m-2 at. Filtering the reservoir water and amending it with chemicals （i.e., CV, NO C, and dissolved organic matter （DOM）） showed significant effects on MMHg PD rate constants. Stepwise regression analysis showed that intensity of solar radiation, suspended particulate matter （SPM）, DOM, CI-, and NO3- were involved in the PD process. Path analysis clarified the relationship between MMHg PD rate constants and environmental variables, as well as the comparative strength of direct and indirect relationships among variables. The results are of great importance for understanding MMHg cycling characteristics in TGR and also facilitate the understanding of the underlying process, MMHg PD, in natural waters.
