Application of diffusive gradient in thin films technique for mercury bioavailability prediction in soil

Dissertation for Degree of Ph.D Application of diffusive gradient in thin films technique for mercury bioavailability prediction in soil Nguyen Huu Viet School of Earth Sciences and Environmental Engineering Gwangju Institute of Science and Technology (GIST) 2021 Application of diffusive gradient in thin films technique for mercury bioavailability prediction in soil Advisor: Professor Seunghee Han By Nguyen Huu Viet School of Earth Sciences and Environmental Engineering Gwangju Institute of Science and Technology (GIST) A thesis submitted to the faculty of Gwangju Institute of Science and Technology in partial fulfillment of the requirement for the degree of Doctor of Philosophy in the School of Earth Sciences and Environmental Engineering Gwangju, Republic of Korea Approved by Professor Seunghee Han Committee Chair Application of diffusive gradient in thin films technique for mercury bioavailability prediction in soil Nguyen Huu Viet Accepted in partial fulfillment of the requirement of the degree of Doctor of Philosophy May 31st, 2021 Dissertation advisor _ Prof Seunghee Han Committee member Prof Kyoung-Woong Kim Committee member Prof Chang-Keun Kang Committee member Prof Yongseok Hong Committee member Prof Nguyen Phuoc Dan PhD./EN 20144049 Nguyen Huu Viet Application of diffusive gradient in thin films technique for mercury bioavailability prediction in soil School of Earth Sciences and Environmental Engineering 2021 P127 Advisor: Seunghee Han (한승희) Abstract The technique of diffusive gradients in thin films (DGT) has been shown to be a promising tool to assess metal bioavailability in soils under laboratory conditions however, its applicability is subject to the type of metal and organism involved The theoretical aspect and application of DGT to measure in situ speciation and bioavailability of diverse metal pollutants in soils were introduced in the first chapter In the second chapter, the accumulated masses of Hg in DGT probes and in the earthworm species Eisenia fetida were monitored for 10 days, to test if the DGT technique can be used as a predicting method for the bioavailability of soil Hg to earthworms The Hg exposure tests were conducted using freshly prepared artificial soils with different peat moss concentrations of 5, 10, 15, and 20% and aged prepared soils with varying pH values of 4.6, 5.6, and 6.2 It is interesting to note that the Hg uptake rates by DGT and earthworms were considerably higher for fresh soils than for aged soils, while pore water (and acid-extractable) Hg concentrations were rather similar between the two types of soils DGT-measured Hg flux used to assess bioavailability in earthworm showed a strong positive correlation with steady-state Hg concentration in earthworm ([earthworm Hg] = 354(DGT−Hg flux) − 34, R = 0.88) The overall results indicate that DGT-measured Hg flux is a better tool than the conventional methods for predicting Hg bioavailability for earthworms inhabiting diverse types of soil In the third chapter, the critical soil characteristics affecting Hg bioavailability to the earthworm Eisenia fetida were evaluated using DGT technique in the metal-contaminated soils collected from Gumu Creek, a i tributary of the Hyeongsan River The correlation analysis showed water holding capacity is the key variable of soil properties related to Hg accumulation in the soil, earthworm, and binding gel Indeed the water-holding capacity played a dual role in the Gumu Creek deposits: increasing the soil Hg concentration and decreasing Hg bioavailability and leachability DGT–Hg flux showed a positive correlated with the Hg concentration in earthworms (r = 0.93) The results of this chapter proved that the DGT method is promising for predicting soil Hg bioavailability to the earthworm Eisenia fetida, and the water-holding capacity simultaneously regulates Hg availability to the DGT and the earthworms In the last chapter, the aging effect of Hg, one of the most important factors controlling Hg bioavailability in soil, was studied using diverse types of field soils Surface soil samples were collected from forestry, agriculture, and riverbank sites (Youngsan and Hyeongsan river) The soil samples were spiked with inorganic Hg(II) and incubated for 1, 3, 5, 8, 15, 25, 40, 60 and 90 days We found that, during the aging process, the proportions of Hg tended to migrate from mobile fraction to the stable binding fractions Effective Hg concentration (C E) was estimated by DGT and DIFS model, as it represents bioavailable fraction of Hg in soils according to the previous literature The effect of Hg aging on CE was evaluated by aging rate constant (k1) obtained by fitting the CE values using pseudo-first order kinetic model Partial Least Square regression (PLSR) model was used to relate various soil properties to the variations of k in those soils PLS model constructed by cross-validation and variable selection routines predicted 31% of k when applied to entire soil samples, but 73 – 92% of k1 was predicted when applied to specific soil type The results showed that variation of k1 was mainly predicted by soil pH and organic matter content The overall results indicate that the combination of DGT technique and PLSR method is a useful tool for evaluating the aging effects on bioavailability of Hg in various types of soils using selected soil properties ii Table of Contents Abstract i List of Figures vii List of Tables x 1.1 Introduction 1.1.1 Mercury cycling in the environment 1.1.2 Hg in soil ecosystem 1.1.3 Bioavailability and toxicity of Hg in soil 1.1.4 DGT technique for Hg measurement 1.2 DGT technique to evaluate lability of Hg in soil 1.2.1 DGT application for labile Hg measurement in soil 1.2.2 DGT technique as a bio-mimics surrogate for mercury bioavailability in soil 1.2.3 Modelling approaches for predicting the bioavailability of Hg in soil using DGT Chapter 2: DGT efficacy tests using earthworm Eisenia fetida grown in artificial soils 12 Abstract 12 2.1 Introduction 13 2.2 Experimental methods 15 2.2.1 DGT probe preparation 15 iii 2.2.2 Preparation and characterization of soils 16 2.2.3 Deployment of DGT probes and earthworms 19 2.2.4 Hg measurement in DGT probes, earthworms, and soils 19 2.2.5 Calculation of CDGT and OCM simulation 21 2.3 Results and discussion 22 2.3.1 Effect of Hg concentration on earthworm and DGT accumulation of Hg 22 2.3.2 Effect of peat moss content on earthworm and DGT accumulation of Hg 26 2.3.3 Effect of soil pH on earthworm and DGT accumulation of Hg 30 2.3.4 Effect of soil aging on earthworm and DGT accumulation of Hg 31 2.3.5 Prediction of Hg bioavailability using DGT and conventional methods 34 2.4 Conclusions 36 Chapter 3: Applying DGT technique for evaluating Hg bioavailability by earthworm Eisenia fetida in natural soils 38 Abstract 38 3.1 Introduction 39 2.2 Materials and Methods 42 2.2.1 DGT unit and earthworm preparation 42 2.2.2 Soil sampling and pre-treatment 43 2.2.3 Deployment of earthworms and DGT units 45 2.2.4 Measurement of soil characteristics 46 iv 2.2.5 Measurement of Hg in resins, earthworms, soils, and headspace air 48 2.2.6 Accumulation factors and statistical analysis 51 2.3 Results and Discussion 52 2.3.1 Soil properties 52 2.3.2 Hg pollution in soils 55 2.3.3 Hg accumulation in earthworms 58 2.3.4 Hg accumulation in DGT 62 2.3.5 Prediction of BAF and DAF using PLSR 64 2.4 Conclusions 67 Chapter 4: Applying DGT techniques for evaluating aging effects of Hg in natural soils 69 Abstract 69 4.1 Introduction 70 4.2 Materials and methods 71 4.2.1 Soil sampling and preparation 72 4.2.2 Incubation method 73 4.2.3 DGT fabrication 74 4.2.4 Measurement of Hg in binding layer and soils 75 4.2.5 Soil properties measurements 75 4.2.6 Effective concentration calculation 78 4.2.7 Kinetic equations for aging and leaching process 79 v 4.2.8 Statistical analysis 80 4.3 Results and discussion 80 4.3.1 Soil characterization 80 4.3.2 Correlation analysis among soil properties 83 4.3.3 Aging effect of Hg on DGT availability and the role of soil properties 85 4.3.4 Prediction of aging rate k1 and PAF using PLS method 88 4.4 Conclusions 92 Chapter 5: Conclusion 94 References 95 vi List of Figures Figure 2.1 The accumulation of Hg in diffusive gradients in thin films (DGT) resin and earthworm tissue as a function of deployment time for aged soils The experimental Hg data were fitted by one compartment model (OCM) Soil composition was 69% sand, 20% kaolinite, 10% peat moss, and 1% CaCO3, and the measured Hg concentration was A 5.2 nmol g-1, B 56 nmol g-1, C 105 nmol g-1, and D 262 nmol g-1 23 Figure 2.2 The accumulation of Hg in diffusive gradients in thin films (DGT) resin and earthworm tissue as a function of deployment time for fresh soils The experimental Hg data were fitted by one compartment model (OCM) Soil composition was 59-74% sand, 20% kaolinite, and 1% CaCO3, and the peat moss content was A 5%, B 10%, C 15%, and D 20% 29 Figure 2.3 The accumulation of Hg in diffusive gradients in thin films (DGT) resin and earthworm tissue as a function of deployment time for fresh soils The experimental Hg data were fitted by one compartment model (OCM) Soil composition was 69% sand, 20% kaolinite, and 10% CaCO3, and the pH of the soil was A 4.6, B 5.6, and C 6.2 30 Figure 2.4 A) Hg in earthworm tissue at steady-state and B) Hg uptake rate by earthworm versus porewater Hg concentration The Hg uptake rate was estimated by k 1×Cs, where Cs is the soil Hg concentration and k1 is the Hg uptake rate constant for earthworm estimated by the one compartment model (OCM), as presented in Table 32 Figure 2.5 A) Hg in earthworm tissue at steady-state and B) Hg uptake rate by earthworm versus acid-extractable Hg concentration The Hg uptake rate was estimated by k1×Cs, where Cs is the soil Hg concentration and k is the Hg uptake rate constant for earthworm estimated by the one compartment model (OCM), as presented in Table 33 Figure 2.6 Correlation of A) Hg in earthworm tissue at steady-state and B) Hg uptake vii He C, Arizono K, Ji H, Yakushiji Y, Zhang D, Huang K, Ishibashi Y (2018a): Spatial distribution characteristics of mercury in the soils and native earthworms (Bimastos parvus) of the leachate-contaminated zone around a traditional landfill Sci Total Environ 636, 1565-1576 He M, Tian L, Braaten HFV, Wu Q, Luo J, Cai LM, Meng JH, Lin Y (2019): Mercury-Organic Matter Interactions in Soils and Sediments: Angel or Devil? Bull Environ Contam Toxicol 102, 621-627 He Y, Guo C, Lv J, Hou S, Zhang Y, Zhang Y, Xu J (2018b): Predicting trace metal bioavailability to chironomids in sediments by diffusive gradients in thin films Sci Total Environ 636, 134-141 He Y, Guo C, Lv J, Hou S, Zhang Y, Zhang Y, Xu J (2018c): Predicting trace metal bioavailability to chironomids in sediments by diffusive gradients in thin films Science of The Total Environment 636, 134-141 Hesterberg D, Chou JW, Hutchison KJ, Sayers DE (2001): Bonding of Hg(II) to reduced organic sulfur in humic acid as affected by S/Hg ratio Environ Sci Technol 35, 2741-5 Higueras P, Oyarzun R, Biester H, Lillo J, Lorenzo S (2003): A first insight into mercury distribution and speciation in soils from the Almaden mining district, Spain Journal of Geochemical Exploration 80, 95-104 Hinton JJ, Veiga MM (2009): Using Earthworms to Assess Hg Distribution and Bioavailability in Gold Mining Soils Soil Sediment Contam 18, 512-524 Hong Y, Dan NP, Kim E, Choi H-J, Han S (2014): Application of diffusive gel-type probes for assessing redox zonation and mercury methylation in the Mekong Delta sediment Environmental Science: Processes & Impacts 16, 1799-1808 Hong YS, Rifkin E, Bouwer EJ (2011): Combination of Diffusive Gradient in a Thin Film probe 103 and IC-ICP-MS for the simultaneous determination of CH3Hg+ and Hg2+ in oxic water Environmental Science & Technology 45, 6429-6436 Hsu-Kim H, Eckley CS, Acha D, Feng X, Gilmour CC, Jonsson S, Mitchell CPJ (2018): Challenges and opportunities for managing aquatic mercury pollution in altered landscapes Ambio 47, 141-169 Jagtap R, Maher W (2015): Measurement of mercury species in sediments and soils by HPLCICPMS Microchemical Journal 121, 65-98 Jiang P, Liu G, Cui W, Cai Y (2018): Geochemical modeling of mercury speciation in surface water and implications on mercury cycling in the everglades wetland Sci Total Environ 640-641, 454-465 Jiskra M, Wiederhold JG, Skyllberg U, Kronberg RM, Hajdas I, Kretzschmar R (2015): Mercury deposition and re-emission pathways in boreal forest soils investigated with Hg isotope signatures Environ Sci Technol 49, 7188-96 Jones R (2010): Day and night: circadian rhythms in worms PLoS Biol 8, e1000511 Kim MK, Zoh KD (2012): Fate and transport of mercury in environmental media and human exposure J Prev Med Public Health 45, 335-43 Kome GK, Enang RK, Yerima BPK, Lontsi MGR (2018): Models relating soil pH measurements in H2O, KCl and CaCl2 for volcanic ash soils of Cameroon Geoderma Regional 14, e00185 Koppel DJ, Adams MS, King CK, Jolley DF (2019): Diffusive Gradients in Thin Films Can Predict the Toxicity of Metal Mixtures to Two Microalgae: Validation for Environmental Monitoring in Antarctic Marine Conditions Environ Toxicol Chem 38, 1323-1333 Kreuzeder A, Santner J, Zhang H, Prohaska T, Wenzel WW (2015): Uncertainty evaluation of the 104 diffusive gradients in thin films technique Environ Sci Technol 49, 1594-602 Lacerda LD, de Souza M, Ribeiro MG (2004): The effects of land use change on mercury distribution in soils of Alta Floresta, Southern Amazon Environ Pollut 129, 247-55 Lanno R, Wells J, Conder J, Bradham K, Basta N (2004): The bioavailability of chemicals in soil for earthworms Ecotoxicol Environ Saf 57, 39-47 Le Roux S, Baker P, Crouch A (2016): Bioaccumulation of total mercury in the earthworm Eisenia andrei Springerplus 5, 681 Li J, Peng Q, Liang D, Liang S, Chen J, Sun H, Li S, Lei P (2016): Effects of aging on the fraction distribution and bioavailability of selenium in three different soils Chemosphere 144, 2351-2359 Liu J, Feng X, Qiu G, Anderson CW, Yao H (2012a): Prediction of methyl mercury uptake by rice plants ( Oryza sativa L.) using the diffusive gradient in thin films technique Environ Sci Technol 46, 11013-20 Liu J, Feng X, Qiu G, Anderson CWN, Yao H (2012b): Prediction of Methyl Mercury Uptake by Rice Plants (Oryza sativa L.) Using the Diffusive Gradient in Thin Films Technique Environmental Science & Technology 46, 11013-11020 Liu M, Luo C, Liu X, Wan G, Dai B (2013): A Study on Measurement of Forest Soil Redox Potential Journal of Analytical Sciences, Methods and Instrumentation 03, 137-151 Lock K, Janssen CR (2001): Cadmium toxicity for terrestrial invertebrates: taking soil parameters affecting bioavailability into account Ecotoxicology 10, 315-22 Lu A, Zhang S, Shan X-q (2005): Time effect on the fractionation of heavy metals in soils Geoderma 125, 225-234 Ma L, Zhong H, Wu YG (2015): Effects of metal-soil contact time on the extraction of mercury 105 from soils Bull Environ Contam Toxicol 94, 399-406 Ma M, Du HX, Wang DY (2019): Mercury methylation by anaerobic microorganisms: A review Critical Reviews in Environmental Science and Technology 49, 1893-1936 Mahbub KR, Krishnan K, Naidu R, Megharaj M (2017): Mercury toxicity to Eisenia fetida in three different soils Environ Sci Pollut Res Int 24, 1261-1269 Mangal V, Stenzler BR, Poulain AJ, Gueguen C (2019): Aerobic and Anaerobic Bacterial Mercury Uptake is Driven by Algal Organic Matter Composition and Molecular Weight Environ Sci Technol 53, 157-165 Mehra OP, Jackson ML (2013): Iron Oxide Removal from Soils and Clays by a Dithionite–Citrate System Buffered with Sodium Bicarbonate In: Ingerson E (Editor), Clays and Clay Minerals Pergamon, pp 317-327 Morel FMM, Kraepiel AML, Amyot M (1998): The chemical cycle and bioaccumulation of mercury Annual Review of Ecology and Systematics 29, 543-566 Ndu U, Christensen GA, Rivera NA, Gionfriddo CM, Deshusses MA, Elias DA, Hsu-Kim H (2018): Quantification of Mercury Bioavailability for Methylation Using Diffusive Gradient in Thin-Film Samplers Environ Sci Technol 52, 8521-8529 Nguyen VH, Yee SK, Hong Y, Moon DH, Han S (2019): Predicting mercury bioavailability in soil for earthworm Eisenia fetida using the diffusive gradients in thin films technique Environ Sci Pollut Res Int 26, 19549-19559 Noh S, Hong YS, Han S (2015): Application of diffusive gradients in thin films and core centrifugation methods to determine inorganic mercury and monomethylmercury profiles in sediment porewater Environmental Toxicology and Chemistry 35, 348-356 Noh S, Hong YS, Han S (2016a): Application of diffusive gradients in thin films and core 106 centrifugation methods to determine inorganic mercury and monomethylmercury profiles in sediment porewater Environmental Toxicology and Chemistry 35, 348-356 Noh S, Hong YS, Han S (2016b): Application of diffusive gradients in thin films and core centrifugation methods to determine inorganic mercury and monomethylmercury profiles in sediment porewater Environ Toxicol Chem 35, 348-56 O'Connor D, Hou D, Ok YS, Mulder J, Duan L, Wu Q, Wang S, Tack FMG, Rinklebe J (2019): Mercury speciation, transformation, and transportation in soils, atmospheric flux, and implications for risk management: A critical review Environ Int 126, 747-761 Obrist D, Kirk JL, Zhang L, Sunderland EM, Jiskra M, Selin NE (2018): A review of global environmental mercury processes in response to human and natural perturbations: Changes of emissions, climate, and land use Ambio 47, 116-140 OECD (2016a): Test No 222: Earthworm Reproduction Test (Eisenia fetida/Eisenia andrei) OECD Guidelines for the Testing of Chemicals, Section OECD (2016b): Test No 222: Earthworm Reproduction Test (Eisenia fetida/Eisenia andrei) Park JD, Zheng W (2012): Human exposure and health effects of inorganic and elemental mercury J Prev Med Public Health 45, 344-52 Pelcova P, Zouharova I, Ridoskova A, Smolikova V (2019): Evaluation of mercury availability to pea parts (Pisum sativum L.) in urban soils: Comparison between diffusive gradients in thin films technique and plant model Chemosphere 234, 373-378 Pelcová P, Dočekalová H, Kleckerová A (2014): Development of the diffusive gradient in thin films technique for the measurement of labile mercury species in waters Analytica Chimica Acta 819, 42-48 Peng X, Fan Y, Jin J, Xiong S, Liu J, Tang C (2017): Bioaccumulation and biomagnification of 107 ultraviolet absorbents in marine wildlife of the Pearl River Estuarine, South China Sea Environmental Pollution 225, 55-65 Philipps RR, Xu X, Mills GL, Bringolf RB (2018): Evaluation of diffusive gradients in thin films for prediction of copper bioaccumulation by yellow lampmussel (Lampsilis cariosa ) and fathead minnow (Pimephales promelas ) Environmental Toxicology and Chemistry Reis AT, Lopes CB, Davidson CM, Duarte AC, Pereira E (2015): Extraction of available and labile fractions of mercury from contaminated soils: The role of operational parameters Geoderma 259, 213-223 Ren L-J, Wen T, Pan W, Chen Y-s, Xu L-L, Yu L-J, Yu C-Y, Zhou Y, An S-Q (2015): Nitrogen removal by ecological purification and restoration engineering in a polluted river CLEAN – Soil, Air, Water 43, 1565-1573 Ridošková A, Ridošková A, Dočekalová H, Pelcová P (2016): Prediction of cadmium, lead and mercury availability to plants: comparison between diffusive gradient in thin films technique measurement and soil grown plants Journal of Elementology 22 Rieder SR, Brunner I, Horvat M, Jacobs A, Frey B (2011): Accumulation of mercury and methylmercury by mushrooms and earthworms from forest soils Environ Pollut 159, 2861-9 Roig N, Sierra J, Ortiz JD, Merseburger G, Schuhmacher M, Domingo JL, Nadal M (2013): Integrated study of metal behavior in Mediterranean stream ecosystems: A case-study Journal of Hazardous Materials 263, Part 1, 122-130 Roulier S, Robinson B, Kuster E, Schulin R (2008): Analysing the preferential transport of lead in a vegetated roadside soil using lysimeter experiments and a dual-porosity model European Journal of Soil Science 59, 61-70 108 Różański SŁ, Castejón JMP, Fernández GG (2016): Bioavailability and mobility of mercury in selected soil profiles Environmental Earth Sciences 75 Schroeder WH, Yarwood G, Niki H (1991): Transformation processes involving mercury species in the atmosphere — results from a literature survey Water Air & Soil Pollution 56, 653666 Selin NE (2009): Global Biogeochemical Cycling of Mercury: A Review Annual Review of Environment and Resources 34, 43-63 Shao DD, Wu SC, Liang P, Kang Y, Fu WJ, Zhao KL, Cao ZH, Wong MH (2012): A human health risk assessment of mercury species in soil and food around compact fluorescent lamp factories in Zhejiang Province, PR China J Hazard Mater 221-222, 28-34 Shetaya WH, Osterwalder S, Bigalke M, Mestrot A, Huang JH, Alewell C (2017): An Isotopic Dilution Approach for Quantifying Mercury Lability in Soils Environmental Science & Technology Letters 4, 556-561 Simpson SL, Yverneau H, Cremazy A, Jarolimek CV, Price HL, Jolley DF (2012a): DGT-induced copper flux predicts bioaccumulation and toxicity to bivalves in sediments with varying properties Environ Sci Technol 46, 9038-46 Simpson SL, Yverneau H, Cremazy A, Jarolimek CV, Price HL, Jolley DF (2012b): DGT-Induced copper flux predicts bioaccumulation and toxicity to bivalves in sediments with varying properties Environmental Science & Technology 46, 9038-9046 Šípková A, Száková J, Hanč A, Tlustoš P (2016): Mobility of mercury in soil as affected by soil physicochemical properties Journal of Soils and Sediments 16, 2234-2241 Sizmur T, Canário J, Gerwing TG, Mallory ML, O'Driscoll NJ (2013): Mercury and methylmercury bioaccumulation by polychaete worms is governed by both feeding 109 ecology and mercury bioavailability in coastal mudflats Environmental Pollution 176, 1825 Skyllberg U, Qian J, Frech W, Xia K, Bleam WF (2003): Distribution of mercury, methyl mercury and organic sulphur species in soil, soil solution and stream of a boreal forest catchment Biogeochemistry 64, 53-76 Skyllberg U, Bloom PR, Qian J, Lin C-M, Bleam WF (2006): Complexation of mercury(II) in soil organic matter:  EXAFS evidence for linear two-coordination with reduced sulfur groups Environmental Science & Technology 40, 4174-4180 Skyllberg U (2011): Chemical Speciation of Mercury in Soil and Sediment, Environmental Chemistry and Toxicology of Mercury, pp 219-258 Streets DG, Horowitz HM, Jacob DJ, Lu Z, Levin L, Ter Schure AFH, Sunderland EM (2017): Total Mercury Released to the Environment by Human Activities Environ Sci Technol 51, 5969-5977 Streets DG, Lu Z, Levin L, Ter Schure AFH, Sunderland EM (2018): Historical releases of mercury to air, land, and water from coal combustion Sci Total Environ 615, 131-140 Tang WL, Liu YR, Guan WY, Zhong H, Qu XM, Zhang T (2020): Understanding mercury methylation in the changing environment: Recent advances in assessing microbial methylators and mercury bioavailability Sci Total Environ 714, 136827 Taylor DL, Linehan JC, Murray DW, Prell WL (2012): Indicators of sediment and biotic mercury contamination in a southern New England estuary Marine Pollution Bulletin 64, 807-819 Teixeira RA, Fernandes AR, Ferreira JR, Vasconcelos SS, Braz AMD (2018): Contamination and Soil Biological Properties in the Serra Pelada Mine - Amazonia, Brazil Revista Brasileira De Ciencia Do Solo 42 110 Teng DY, Mao K, Ali W, Xu GM, Huang GP, Niazi NK, Feng XB, Zhang H (2020): Describing the toxicity and sources and the remediation technologies for mercury-contaminated soil Rsc Advances 10, 23221-23232 Turull M, Fontas C, Diez S (2019a): Conventional and novel techniques for the determination of Hg uptake by lettuce in amended agricultural peri-urban soils Sci Total Environ 668, 4046 Turull M, Fontas C, Diez S (2019b): Diffusive gradient in thin films with open and restricted gels for predicting mercury uptake by plants Environmental Chemistry Letters 17, 1353-1358 UNEP (2008): The Global atmospheric mercury assessment: Sources, emissions and transport , UNEP - Chemicals, Geneva UNEP (2013): Global Mercury Assessment 2013: Sources, Emissions, Releases and Environmental Transport, UNEP Chemicals Branch, Geneva, Switzerland UNEP (2019): Global Mercury Assessment 2018, UN Environment Programme, Chemicals and Health Branch Geneva, Switzerland Vandenhove H, Antunes K, Wannijn J, Duquène L, Van Hees M (2007): Method of diffusive gradients in thin films (DGT) compared with other soil testing methods to predict uranium phytoavailability Science of The Total Environment 373, 542-555 Wang X, Tam NF, Fu S, Ametkhan A, Ouyang Y, Ye Z (2014a): Selenium addition alters mercury uptake, bioavailability in the rhizosphere and root anatomy of rice (Oryza sativa) Ann Bot 114, 271-8 Wang X, Yuan W, Lin CJ, Zhang L, Zhang H, Feng X (2019): Climate and Vegetation As Primary Drivers for Global Mercury Storage in Surface Soil Environ Sci Technol 53, 10665-10675 Wang Y, Greger M (2006): Use of iodide to enhance the phytoextraction of mercury-contaminated 111 soil Sci Total Environ 368, 30-9 Wang Z, Zhao P, Yan C, Chris VD, Yan Y, Chi Q (2014b): Combined use of DGT and transplanted shrimp (Litopenaeus vannamei) to assess the bioavailable metals of complex contamination: implications for implementing bioavailability-based water quality criteria Environmental Science and Pollution Research 21, 4502-4515 Warnken KW, Zhang H, Davison W (2006a): Accuracy of the diffusive gradients in thin-films technique: diffusive boundary layer and effective sampling area considerations Anal Chem 78, 3780-7 Warnken KW, Zhang H, Davison W (2006b): Accuracy of the diffusive gradients in thin-films technique:  Diffusive boundary layer and effective sampling area considerations Analytical Chemistry 78, 3780-3787 Wen B, Hu X-y, Liu Y, Wang W-s, Feng M-h, Shan X-q (2004): The role of earthworms (Eisenia fetida) in influencing bioavailability of heavy metals in soils Biology and Fertility of Soils 40, 181-187 WHO (2019): Mercury and health World Health Organization https://www.who.int/newsroom/fact-sheets/detail/ Xu J, Bravo AG, Lagerkvist A, Bertilsson S, Sjoblom R, Kumpiene J (2015): Sources and remediation techniques for mercury contaminated soil Environ Int 74, 42-53 Xu Q, Gao L, Peng W, Gao B, Xu D, Sun K (2018): Assessment of labile Zn in reservoir riparian soils using DGT, DIFS, and sequential extraction Ecotoxicology and Environmental Safety 160, 184-190 Xu X, Peck E, Fletcher DE, Korotasz A, Perry J (2020): Limitations of Applying Diffusive Gradients in Thin Films to Predict Bioavailability of Metal Mixtures in Aquatic Systems 112 with Unstable Water Chemistries Environ Toxicol Chem 39, 2485-2495 Yang L, Zhang Y, Wang F, Luo Z, Guo S, Strahle U (2020): Toxicity of mercury: Molecular evidence Chemosphere 245, 125586 Yang Y, Liang L, Wang D (2008): Effect of dissolved organic matter on adsorption and desorption of mercury by soils Journal of Environmental Sciences 20, 1097-1102 Yin H, Fan C (2011): Dynamics of Reactive Sulfide and its Control on Metal Bioavailability and Toxicity in Metal-Polluted Sediments from Lake Taihu, China Archives of Environmental Contamination and Toxicology 60, 565-575 Yin H, Cai Y, Duan H, Gao J, Fan C (2014a): Use of DGT and conventional methods to predict sediment metal bioavailability to a field inhabitant freshwater snail (Bellamya aeruginosa) from Chinese eutrophic lakes Journal of Hazardous Materials 264, 184-194 Yin RS, Feng XB, Li XD, Yu B, Du BY (2014b): Trends and advances in mercury stable isotopes as a geochemical tracer Trends in Environmental Analytical Chemistry 2, 1-10 Yin RS, Gu CH, Feng XB, Hurley JP, Krabbenhoft DP, Lepak RF, Zhu W, Zheng LR, Hu TD (2016): Distribution and geochemical speciation of soil mercury in Wanshan Hg mine: Effects of cultivation Geoderma 272, 32-38 Yu H, Huang X, Ning JG, Zhu BL, Cheng Y (2014): Effect of cation exchange capacity of soil on stabilized soil strength Soils Found 54, 1236-1240 Yu K, Rinklebe J (2015): Soil Redox Potential and pH Controllers, Methods in Biogeochemistry of Wetlands SSSA Book Series, pp 107-116 Zarrouk S, Bermond A, Kolsi Benzina N, Sappin-Didier V, Denaix L (2014): Diffusive gradient in thin-film (DGT) models Cd and Pb uptake by plants growing on soils amended with sewage sludge and urban compost Environmental Chemistry Letters 12, 191-199 113 Zhang H, Davison W (1995): Performance Characteristics of Diffusion Gradients in Thin Films for the in Situ Measurement of Trace Metals in Aqueous Solution Analytical Chemistry 67, 3391-3400 Zhang H, Davison W (2000): Direct in situ measurements of labile inorganic and organically bound metal species in synthetic solutions and natural waters using diffusive gradients in thin films Analytical Chemistry 72, 4447-4457 Zhang H, Zhao F-J, Sun B, Davison W, McGrath SP (2001): A New Method to Measure Effective Soil Solution Concentration Predicts Copper Availability to Plants Environmental Science & Technology 35, 2602-2607 Zhang HL, Zhao ZF, Ma GF, Sun LN (2020): Quantitative evaluation of soil anti-erodibility in riverbank slope remediated with nature -based soil bioengineering in Liaohe River, Northeast China Ecological Engineering 151, 105840 Zhang L, Verweij RA, Van Gestel CAM (2019): Effect of soil properties on Pb bioavailability and toxicity to the soil invertebrate Enchytraeus crypticus Chemosphere 217, 9-17 Zhao B, O'Connor D, Shen Z, Tsang DCW, Rinklebe J, Hou D (2020): Sulfur-modified biochar as a soil amendment to stabilize mercury pollution: An accelerated simulation of long-term aging effects Environ Pollut 264, 114687 Zhong H, Wang WX (2009): Inorganic mercury binding with different sulfur species in anoxic sediments and their gut juice extractions Environ Toxicol Chem 28, 1851-7 114 Acknowledgement Thank you to my supervisor, Professor Seunghee Han, for your patience, guidance, and support I have benefited greatly from your wealth of knowledge and meticulous editing I am extremely grateful that you took me on as a student and continued to have faith in me over the years Thank you to my committee members, Professor Yongseok Hong, Professor Chang-Keun Kang, Professor Kyoung-Woong Kim and Professor Nguyen Phuoc Dan Your encouraging words and thoughtful, detailed feedback have been very important to me Thank you to the labmembers, who so generously took time out of their schedules to assist me during project Their company in sampling and laboratory will be always remembered Last but not the least I would also like to thank all my friend, family members for encouraging and supporting me whenever I needed them 115 CURRICULUM VITAE Name: Nguyen Huu Viet Birth date: June 3rd, 1986 Birthplace: Tuy Hoa city, Phu Yen Province, Vietnam Education: 2004 – 2010: Ho Chi Minh University of Technology (HCMUT) Bachelor of Engineering, Division of Physio-chemical Engineering Faculty of Chemical Engineering 2014 – 2021: Gwangju Institute of Science and Technology (GIST) Doctor of Philosophy, Environmental Sciences School of Earth Sciences and Environmental Engineering Trace Metal Biogeochemistry Laboratory Selected Publications Nguyen VH, Yee SK, Hong Y, Moon DH, Han S (2019): Predicting mercury bioavailability in soil for earthworm Eisenia fetida using the diffusive gradients in thin films technique Environ Sci Pollut Res Int 26, 19549-19559 Nguyen VH, Seon JY, Qasim GH, Fareed H, Hong Y, Han S (2021): Applying the diffusive gradient in thin films method to assess soil mercury bioavailability to the earthworm Eisenia fetida Environ Sci Pollut Res Int 116 Shin H, Kim J, Kim D, Nguyen VH, Lee S, Han S, Lim J, Char K (2018): Aqueous "polysulfideene" polymerization for sulfur-rich nanoparticles and their use in heavy metal ion remediation Journal of Materials Chemistry A 6, 23542-23549 Qasim GH, Nguyen VH, Lee S, Lee W, Han S (2020): Countereffect of glutathione on divalent mercury removal by nanoscale zero-valent iron in the presence of natural organic matter J Hazard Mater 398, 122874 Selected presentations Poster presentation Nguyen Huu Viet, Seunghee Han 2016 Application of the Diffusive Gradients in Thin Films Induced Fluxes in Soils (DIFS) Model to Assess Resupply Kinetics of Uranium: Effects of Organic Matter and Iron Oxides Goldschmidt Conference at Yokohama, Japan June 26 - July 1, 2016 Nguyen Huu Viet, Seunghee Han 2019 Application of diffusive gradient in thin films (DGT) method to assess bioavailable Hg in artificial and natural soils 14 th International Conference on Mercury as a Global Pollutant (ICMGP) 8-13 September 2019, Krakow, Poland 117 ... 20144049 Nguyen Huu Viet Application of diffusive gradient in thin films technique for mercury bioavailability prediction in soil School of Earth Sciences and Environmental Engineering 2021 P127 Advisor:.. .Application of diffusive gradient in thin films technique for mercury bioavailability prediction in soil Advisor: Professor Seunghee Han By Nguyen Huu Viet School of Earth Sciences... diffusive gradient in thin films technique for mercury bioavailability prediction in soil Nguyen Huu Viet Accepted in partial fulfillment of the requirement of the degree of Doctor of Philosophy May