Luận án tiến sĩ: Vận chuyển đồng và cố định chì bằng nanoparticles sắt phosphate

FATE, TRANSPORT, AND ENVIRONMENTAL AVAILABILITY OF CU(II) APPLIED IN CATFISH AQUACULTURE PONDS AND ENHANCED IMMOBILIZATION OF SOIL-BOUND LEAD USING A NEW CLASS OF STABILIZED IRON PHOSPHATE NANOPARTICLES Ruiqiang Liu A Dissertation Submitted to the Graduate Faculty of Auburn University in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy Auburn, Alabama May 10, 2007 UMI Number: 3245484 UMI Microform 3245484 Copyright 2007 by ProQuest Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest Information and Learning Company 300 North Zeeb Road P.

Box 1346 Ann Arbor, MI 48106-1346 FATE, TRANSPORT, AND ENVIRONMENTAL AVAILABILITY OF CU(II) APPLIED IN CATFISH AQUACULTURE PONDS AND ENHANCED IMMOBILIZATION OF SOIL-BOUND LEAD USING A NEW CLASS OF STABILIZED IRON PHOSPHATE NANOPARTICLES Except where reference is made to the work of others, the work described in this dissertation is my own or was done in collaboration with my advisory committee. This dissertation does not include proprietary or classified information. Ruiqiang Liu Certificate of Approval: Mark O. Barnett Dongye Zhao, Chairman Associate Professor Associate Professor Civil Engineering Civil Engineering Claude E.

Shaw Professor, Associate Professor Fisheries and Allied Agronomy and Soils Aquacultures Yucheng Feng Joe F. Pittman Associate Professor Interim Dean Agronomy and Soils Graduate School FATE, TRANSPORT, AND ENVIRONMENTAL AVAILABILITY OF CU(II) APPLIED IN CATFISH AQUACULTURE PONDS AND ENHANCED IMMOBILIZATION OF SOIL-BOUND LEAD USING A NEW CLASS OF STABILIZED IRON PHOSPHATE NANOPARTICLES Ruiqiang Liu Permission is granted to Auburn University to make copies of this dissertation at its discretion, upon request of individuals or institutions and at their expense. The author reserves all publication rights. Signature of Author Date of Graduation iii VITA Ruiqiang Liu, son of Wuwang Liu and Xuede Zhang, was born in Taiyuan, Shanxi, China on February 3, 1971.

He earned his bachelors degree in Environmental Engineering from Taiyuan University of Technology, China in 1994. He earned his M. in environmental engineering from the same university in 1997. Since August 2002, he has been a Ph.

student in the Department of Civil Engineering. During his stay at Auburn, he has produced one U. patent (pending), four journal papers (two published, one in review, another being submitted) and two technical reports, and delivered five presentations at various national meetings. iv DISSERTATION ABSTRACT FATE, TRANSPORT, AND ENVIRONMENTAL AVAILABILITY OF CU(II) APPLIED IN CATFISH AQUACULTURE PONDS AND ENHANCED IMMOBILIZATION OF SOIL-BOUND LEAD USING A NEW CLASS OF STABILIZED IRON PHOSPHATE NANOPARTICLES Ruiqiang Liu Doctorate of Philosophy, May 10, 2007 (M., Taiyuan University of Technology, 1997) (B., Taiyuan University of Technology, 1994) 226 Typed Pages Directed by Dongye Zhao Copper sulfate has been the most commonly used algaecide for about a century in the U.

to control the off-flavor problem caused by blue-green algae in channel catfish (Ictalurus punctatus) ponds. In 2001, the ~80,000 hectares of channel catfish ponds in the U. received a total dose of 4,000,000 kg of CuSO4·5H2O or 1,000,000 kg of Cu2+. However, no detailed studies have been available pertaining to the potential adverse impacts of the copper applied in catfish ponds on human and environmental health.

A pilot-scale study and various field measurements at commercial ponds were conducted to investigate the environmental fate of copper applied as an algaecide in catfish ponds. In the pilot study, a total of 774 g Cu(II) were applied to an experimental catfish pond over a period of 16 summer weeks. Copper mass balance indicated that v virtually all Cu(II) applied was retained in the sediment.01% of the total Cu applied was taken up by fish and 0.1% remained in pond water. Data from three commercial fishponds of different ages (1-25 years) and with different sediment types (acidic, neutral and calcareous) supported the pilot-scale observation.

Field monitoring of groundwater quality suggested that the copper leaching into the groundwater surrounding the ponds was insiginificant. Sediments taken from the three commercial catfish ponds were studied for content, leachability, bioaccessibility, and speciation of sediment-bound Cu(II). Results showed that copper was concentrated in the top 10 cm of the sediments. Leachability tests based on the toxicity characteristic leaching procedure (TCLP) showed ~1-8% of sediment- bound copper was leachable, while the bioaccessible copper, determined following a physiological based extraction test (PBET) procedure, accounted for up to ~40-80% of total Cu.

Becasue of the high redox potential in the surface sediments, acid volatile sulfide was not a significant sink for copper. Tests following a sequential extraction method revealed that the residual phase copper (i. Cu bound in the lattices of primary and secondary minerals) was the major Cu fraction in the ponds with acidic and calcareous sediments but carbonate-bound, Fe/Mn oxide-bound and organically bound Cu, as well as the residual fraction, seemed equally important in the pond with neutral sediment. Effects of various soil fractions and soil compositions on the leachability and bioaccessibility of soil-bound Cu were investigated with three representative soils (calcareous, neutral, and acidic).

The synthetic precipitation leaching procedure (SPLP) was used to assess the metal leachability, the PBET was used to assess the vi bioaccessibility, and a selective dissolution approach was applied to fractionate the soil fractions. Data showed that soil carbonates played an important role in Cu desorption from soil. The leachability of Cu bound in carbonate-rich soils was less than that in soils with lower carbonate content. However, the bioaccessibility of copper in carbonate-rich soils was greater than that for soils with low carbonate content.

Leachability and bioaccessibility of Cu in different particle size fractions fractionated on were found to be correlated with the carbonate contents in each fraction. Results also showed Fe/Mn oxides, organic matter and clay minerals are responsible for Cu retention under acidic leaching conditions, and clay minerals consistently showed the strongest affinity for Cu. This study developed a new class of iron phosphate (vivianite) nanoparticles, prepared with sodium carboxymethyl cellulose (CMC) as a stabilizer, and tested the feasibility of applying the nanoparticles for in-situ immobilization of lead (Pb2+) in soils. TEM measurements indicated that the mean particle size was about 8.

Batch test results showed that the CMC-stabilized nanoparticles can effectively reduce the TCLP leachability and PBET-based bioaccessibility of Pb2+ in the 3 representative soils. When the soils were treated with the nanoparticles at a dosage ranging from 0.0 mg as PO43-/g-soil for 56 days, the TCLP leachability of Pb2+ was reduced by up to 95%, whereas the bioaccessibility of Pb2+ in the soils was reduced by 31~47%. vii Style manual or journal used Water, Air and Soil Pollution Computer Software used Microsoft Excel 2003, Microsoft Word 2003, Sigmaplot 8.0, and Visual MINTEQ 2. viii ACKNOWLEDGMENTS The author would like to express his sincere and profound gratitude to Dr.

Dongye Zhao for his support, invaluable advice, guidance and patience throughout the duration of his studies. The author would also like to extend his great appreciation to the members of his advisory committee: Dr. Boyd and Dr. Yucheng Feng for their constant support throughout this research.

Many advices from my late committee member, Dr. Jim F Adams, were also unforgettable. Great thanks are due to Dr. Jinling Zhuang and Dr.

Junchen Liu for providing and operating the related research facilities. Special thanks are also extended to Dr. Ming- Kuo Lee for his assistance in dissertation writing. The author would also like to express his deepest appreciation to his parents and family for their versatile and continuous support.

The author has special appreciation to his wife, Miao Guo and his son Eric Liu for bringing a lot into his life that he stands too short to count. This work was partially funded by Auburn University Environmental Institute, USGS Alabama Water Resources Research Institute, Auburn University Highway Research Center and the Strategic Environmental Research and Development Program (SERDP) under the direction of Dr. ix TABLE OF CONTENTS LIST OF TABLES………………………………………………………………. xii LIST OF FIGURES.

FATE AND TRANSPOT OF COPPER APPLIED IN CHANNEL CATFISH PONDS ……. MATERIALS AND METHODS……………………………………. RESULTS AND DISCUSSION………………………………………. THE LEACHABILITY, BIOACCESSIBILITY, AND SPECIATION OF CU IN THE SEDIMENT OF CHANNEL CATFISH PONDS ……….

MATERIALS AND METHODS……………………………………… 45 3. RESULTS AND DISCUSSION………………………………………. 74 CHAPTER IV INFLUENCES OF VARIOUS SOIL FRACTIONS ON THE LEACHABILITY AND BIOACCESSIBILITY OF CU(II) IN SOILS……. MATERIALS AND METHODS……………………………………… 79 3.

RESULTS AND DISCUSSION………………. REDUCING LEACHABILITY AND BIOACCESSIBILITY OF LEAD IN SOILS USING A NEW CLASS OF STABILIZED IRON PHOSPHATE NANOPARTICLES………………………………………. MATERIALS AND METHODS……………………………………… 116 3. RESULTS AND DISCUSSION……………………………………….

OVERALL CONCLUSIONS AND FUTURE WORK………… 164 1. RECOMMENDATIONS FOR FUTURE WORK……………………. 193 xi LIST OF TABLES Table 2. Pond water quality and soil property data for the experimental pond and the commercial ponds.

Summary of Cu budget calculations ……. Cu concentrations in tissues of the catfish raised in commercial ponds ……………………………………………. Pond water quality and soil property data for the commercial catfish ponds ………………………………………………………………………… 47 Table 3. Experimental conditions for sequential extraction procedures ….

Chemical characteristics of the sediments at different sites and depths ………………………………………………………………………. Salient physical and chemical properties of soils used in study ………………………………………………………………………. Correlating SPLP-leachable Cu concentration with total Cu in soils… 90 Table 4. Correlating PBET-leachable Cu concentration with total Cu in soils….

Dissolution of various soil minerals under SPLP and PBET conditions and their effects on final pH……………………………………… 110 Table 5. Salient physical and chemical properties of soils used in study. Experimental conditions for sequential extraction of Pb from soils. Changes of Pb concentration in TCLP extract with time after soils were amended with vivianite nanoparticles in Case 1 (nanoparticle suspension -to-soil ratio = 2:1 mL/g)………………………………………….

Changes of Pb concentration in the TCLP extract with time after soils were amended with vivianite nanoparticles in Case 2 (nanoparticle suspension-to-soil ratio = 10:1 mL/g)………………………. Pb concentrations in PBET extracts for three soils before and after nanoparticle treatments……………………………………. Effects of chloride on TCLP leachable Pb in soils amended with stabilized vivianite nanoparticles……………………………………………. Phosphate leached from soils after being amended with vivianite nanoparticle suspension or sodium phosphate (NaH2PO4) solution for 7 days ……………………………………………………….

Changes of Pb concentrations in the TCLP extracts with treatment time after soils were amended with 1.43 mM FeS nanoparticle suspension ………………………………………………………………. Changes of Pb concentrations in the TCLP extracts with treatment time after soils were amended with 30 mM magnetite nanoparticle suspension …………………………………………………………………. 160 xiii LIST OF FIGURES Figure 2. A plan view (not to scale) of the experimental pond and location of the water and sediment sampling points………………………………….

Transient change in concentration of total Cu in pond water at Points A, C and E following a Cu application ………. Transient change in concentration of dissolved Cu in pond water at Points A, C and E following a Cu application……………………………….3 Dynamic profiles of DO and pH in pond water following a copper application. Copper added at t = 0. Accumulation of Cu in sediment at point E (a) during the Cu application season ………………………………………………………….

Accumulation of Cu in sediment at point A (b) during the Cu application season ……………………. Accumulation of Cu in sediment at point D (c) during the Cu application season …………………………………………………………… 25 Figure 2. Vertical distributions of Cu in sediment at Point B at the beginning, middle and end of the study period …………………………………………. Changes in copper concentrations in selected fish tissues with time …………….

Vertical distribution in Cu concentration and bulk density with depth of the pond sediment/bottom soil for 1-year pond……………………. Vertical distribution in Cu concentration and bulk density with depth of the pond sediment/bottom soil for 5-year pond……………………. Vertical distribution in Cu concentration and bulk density with depth of the pond sediment/bottom soil for 25-year pond …………………. Spatial distributions of Cu in the 5-year pond sediment…………….

Spatial distributions of Cu in the 1-year and 25-year pond sediments……………………………………………………………………. Spatial distributions of acid volatile sulfide (AVS) and simultaneously extracted Cu (SEMCu) in the 1-year pond sediment…………. Spatial distributions of acid volatile sulfide (AVS) and simultaneously extracted Cu (SEMCu) in the 5-year pond sediment…………. Spatial distributions of acid volatile sulfide (AVS) and simultaneously extracted Cu (SEMCu) in the 25- year pond sediment……….

Spatial variations of the TCLP leachable Cu in the pond sediments… 62 Figure 3.