Source: MICHIGAN STATE UNIV submitted to NRP
MOVEMENT AND DEGRADATION OF ORGANIC CONTAMINANTS AND PESTICIDES IN SOILS AND SEDIMENTS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
HATCH
Reporting Frequency
Annual
Accession No.
0137713
Grant No.
(N/A)
Cumulative Award Amt.
(N/A)
Proposal No.
(N/A)
Multistate No.
(N/A)
Project Start Date
Mar 1, 2011
Project End Date
Feb 28, 2016
Grant Year
(N/A)
Program Code
[(N/A)]- (N/A)
Recipient Organization
MICHIGAN STATE UNIV
(N/A)
EAST LANSING,MI 48824
Performing Department
Plant, Soil and Microbial Science
Non Technical Summary
The following outcomes/impacts and benefits have accrued from the project: Provide data to regulatory agencies that can help set reliable dioxin bioavailabilities for contaminated soils and sediments. Accurate values are needed to understand soil pathways of exposure for exposure/risk models and for setting regulatory/remediation goals for soils. To establish whether in vitro bioaccessibility tests can be used to provide reliable bioavailability values for risk assessment. Understand the role of natural formation of dioxins and predioxins as an ongoing environmental process leading to unexpected accumulations of dioxins. Understanding the strengths of sorption to each relevant geosorbent can help understand the potential need for remediation of soils/sediments and assist in setting priorities for cleanup of contaminated sites. With huge production of chars in the planning stages for various bioenergy/C sequestration schemes, it is worth examining the possibility of using these byproducts as soil amendments to reduce the bioavailabilities of PCDDs. Adding 1-3% activated C to several sediments typically resulted in a >70% reduction in biouptake of PCBs or PCDDs by benthic organisms, and the cost of such in-situ remediation is estimated at $75,000/ha versus $2.5M-$15M/ha for full dredging and disposal.
Animal Health Component
(N/A)
Research Effort Categories
Basic
(N/A)
Applied
(N/A)
Developmental
(N/A)
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
13301102000100%
Knowledge Area
133 - Pollution Prevention and Mitigation;

Subject Of Investigation
0110 - Soil;

Field Of Science
2000 - Chemistry;
Goals / Objectives
The goals and objectives of the project are: 1. To determine the magnitude of dioxin sorption by carbonaceous geosorbents (GCs), soil amorphous organic matter (AOM) and clay minerals, and the factors affecting the sorption. The principal goal is to compare the sequestration of PCDDs by the key geosorbents in soils/sediments. I also propose to determine the energies of PCDD sorption by CGs, and to evaluate the factors attenuating PCDD sorption. 2. To determine the differential bioaccessibilities and bioavailabilities of PCDDs sorbed to each of the key geosorbent phases in soils and sediments. I propose to use PCDDs associated with CGs, AOM and clay minerals (as prepared in Aim 1 above) in three types of experiments: 2a) PCDD-loaded geosorbents will undergo physiologically based extraction tests (PBETs) in order to quantify bioaccessibility. These in vitro bioaccessibility values will be compared with in vivo bioavailability endpoints measured in animal feeding studies. 2b) Mice will be fed PCDDs that have been sequestered in each of the key geosorbents. Endpoints: Suppression of immune response in mice and direct or indirect measures of transport of PCDDs to mouse tissues (performed in Kaplan laboratory at Michigan State University). 2c) Bacterial cultures will be presented with PCDDs on each of the key geosorbents in order to explore the effects of sorption on microbial bioavailability. Endpoints: Functional genomic responses of bacteria to geosorbents or to sorbed PCDDs. 3. To test the hypothesis that relationships (developed in Aims 1 and 2) between PCDD sorption by individual geosorbents and subsequent bioaccessibility/bioavailability of these bound PCDDs can be extended to predict toxicity responses to whole soils and sediments. The goal is to build a more mechanistic understanding (from the structure-activity work on individual isomers and geosorbents) of the relationship between soil composition and the human health and ecological risks posed by a given total PCDD load. 4. To explore/establish the formation and mechanisms for formation of dioxin congeners in clay interlayers. A combined wet chemistry, spectroscopic and computational approach will be brought to these elements. Specifically, I seek to understand (4a) the relationship between specific chlorophenol precursors and the quantity of PCDDs/predioxins formed, (4b) the underlying mechanistic basis for these reactions including the central roles of the Fe-center and the clay surfaces, (4c) the effect of clay type (source of charge deficit and structural Fe content), (4d) the movement of PCDDs/predioxins from the interlayer regions where they form to other sorbent compartments, and (4e) the bioaccessibility/bioavailability of these products.
Project Methods
The work proposed is mechanism based: We will couple various forms of spectroscopy (FTIR, NMR, ESR) and molecular simulation with detailed macroscopic sorption measurements and XRD to determine molecular scale mechanisms for sorption. Solid phase microextration (SPME) techniques will be employed to extract low levels (ppt-ppb) of analytes which will be quantified using HPLC, GC, GC/MS and LC/MS/MS. Bioavailability of sorbed contaminants to microbes will be studied using molecular biology tools such as gene expression analysis and reporter systems. Oral bioavailability of soil-sorbed pesticides will be evaluated using an in vitro extraction fluid that simulates the human gastrointestinal tract.

Progress 03/01/11 to 02/28/16

Outputs
Target Audience:Environmental scientists and engineers, environmental consulting firms, regulatory agencies. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Training of graduate students and post-doctoral research associates. How have the results been disseminated to communities of interest?Dr. Boyd has been designated "Highly Cited Researcher" in the category of Environmental Science by the Institute for Scientific Information (ISI). This is based on literature citations of Dr. Boyd's published work by other researchers in the their subsequently published papers. The Highly Cited Researcher designation is given to less than one half of one percent of all publishing authors. It is accepted as the "gold standard" for objectively measuring research impact. Dr. Boyd published work has received over 10,000 citations in the scientific literature. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? The effect of contaminant sorption on bioavailability and hence exposure/ toxicity is needed to establish more realistic cleanup criteria for soils and sediments such as those found at Superfund sites. Additionally, the use of sorbent amendments, as for example with activated carbon, to sequester contaminants in forms that reduce or eliminate bioavilability is an exciting new direction in the remediation of contaminated soils and sediments. We have shown for the first time that activated carbon can sequester 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in a form that eliminates its bioavailability to a mammalian (mouse) model. This supports the concept of using sorbent amendments as a new direction in the management of TCDD contaminated soils/sediments, which offers cost savings compared to conventional technologies.

Publications

  • Type: Journal Articles Status: Accepted Year Published: 2016 Citation: Benli Chai, Tamara Tsoi, Shoko Iwai, Cun Liu, Jordan Fish, Cheng Gu, Timothy A. Johnson, Gerben Zylstra, Brian Teppen, Hui Li, Syed Hashsham, Stephen Boyd, James Cole, and James Tiedje, 2016, Sphingomonas wittichii strain RW1 Genome-Wide Gene Expression Shifts in Response to Dioxins and Clay. PlosOne. 11(6): e0157008.
  • Type: Journal Articles Status: Under Review Year Published: 2016 Citation: Stephen Boyd, Brett Sallach, Yingjie Zhang, Robert Crawford, Hui Li, Cliff Johnson, Brian Teppen, and Norbert Kaminski, 2016, Sequestration of TCDD by activated carbon eliminates bioavailability and the suppression of immune function in mine. Environmental Science and Technology.


Progress 10/01/14 to 09/30/15

Outputs
Target Audience: Nothing Reported Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest? Nothing Reported What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? Consideration of soil organic matter and clays as sorptive phases for pesticides in soils will allow development of better pesticide fate and transport models. Polychlorinated dioxins, especially octachlorodioxin and the highly toxic 2,3,7,8- tetrachlorodioxin, are found at inexplicably high levels even in "pristine" rural and agricultural soils, but their origins are unknown. The potential for clay-mediated in-situ formation of dioxins has important implications for past, present and future contamination of rural soils. Dr. Boyd has been designated "Highly Cited Researcher" in the category of Environmental Science by the Institute for Scientific Information (ISI). This is based on literature citations of Dr. Boyd's published work by other researchers in their subsequently published papers. The Highly Cited Researcher designation is given to less than onehalf of one percent of all publishing authors. It is accepted as the "gold standard" for objectively measuring research impact.

Publications

  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Haoting Tian, Yong Guo, Bo Pan, Cheng Gu, Hui Li, and Stephen A. Boyd, 2015, Enhanced Photoreduction of Nitro-aromatic Compounds by Hydrated Electrons Derived from Indole on Natural Montmorillonite. Environmental Science and Technology 49:7784-7792.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Cun Liu, Cheng Gu, Kai Yu, Hui Li, Brian J. Teppen, Cliff T. Johnston, Stephen A. Boyd, and Dongmei Zhou, 2015, Integrating structural and thermodynamic mechanisms for sorption of PCBs by montmorillonite. Environmental Science and Technology 49:2796-2805.
  • Type: Journal Articles Status: Under Review Year Published: 2015 Citation: Benli Chai, Tamara Tsoi, Shoko Iwai, Cun Liu, Jordan Fish, Cheng Gu, Tim Johnson, Gerben Zylstra, Brian Teppen, Hu Li, Syed Hashsham, Stephen Boyd, James Cole, and James Tiedje, 2015, Sphingomonas wittichii strain RW1 genome-wide gene expression shifts in response to dioxins and clay. PlosOne.


Progress 10/01/13 to 09/30/14

Outputs
Target Audience: Other researchers in the same or ancillary fields of study. Designation as "Highly Cited Author" demonstrates the high degree to which this audience is being reached. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Education through publications. How have the results been disseminated to communities of interest? Through publications. What do you plan to do during the next reporting period to accomplish the goals? The overall objective of this project is to evaluate the transport, transformations and bioavailability of organic contaminants and pesticides in soils, sediments and aquifers. Significant progress has been made in several areas of research including: (1) delineation of the relative roles and mechanistic function of clays and organic matter in the retention and transformations of pesticides and related organic contaminants by soils, (2) determining the effects of sorption by soil on the bioavailability of pesticides to mammalian (mouse) model and (3) evaluating the in-situ formation of dioxins on soil clays, including the most toxic species, i.e., 2,3,7,8-TCDD. We will continue with these objectives.

Impacts
What was accomplished under these goals? Consideration of soil organic matter and clays as sorptive phases for pesticides in soils will allow development of better pesticide fate and transport models. Polychlorinated dioxins, especially octachlorodioxin and the highly toxic 2,3,7,8- tetrachlorodioxin, are found at inexplicably high levels even in "pristine" rural and agricultural soils, but their origins are unknown. The potential for clay-mediated in-situ formation of dioxins has important implications for past, present and future contamination of rural soils. Dr. Boyd has been designated "Highly Cited Researcher" in the category of Environmental Science by the Institute for Scientific Information (ISI). This is based on literature citations of Dr. Boyd's published work by other researchers in their subsequently published papers. The Highly Cited Researcher designation is given to less than onehalf of one percent of all publishing authors. It is accepted as the "gold standard" for objectively measuring research impact.

Publications

  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Cun, Liu, Cheng Gu, Kai Yu, Hui, Li, Brian Teppen, Cliff Johnston, Stephen Boyd, and Dongmei Zhou. 2014. Molecular Mechanisms of Coplanar PCB Interactions with Montmorillonite. Environ. Sci. Technol. Submitted. Yingjie Zhang, Stephen Boyd, Brian Teppen, James Tiedje, and Hui Li. 2014. Organic Acids Enhance Bioavailability of Tetracycline in Water to Escherichia coli for Uptake and Expression of Antibiotic Resistance. Water Research, 65:98-106. Yingjie Zhang, Stephen Boyd, Brian Teppen, James Tiedje, and Hui Li. 2014. Role of Tetracycline Speciation in Bioavailability to Escherichia coli for Uptake and Expression of Antbiotic Resistance. Environmental Science and Technology. 48:4893-4900.


Progress 01/01/13 to 09/30/13

Outputs
Target Audience: Other researchers in the same or ancillary fields of study. Designation as "Highly Cited Author" demonstrates the high degree to which this audience is being reached. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Education through publications. How have the results been disseminated to communities of interest? Throught publications. What do you plan to do during the next reporting period to accomplish the goals? The overall objective of this project is to evaluate the transport, transformations and bioavailability of organic contaminants and pesticides in soils, sediments and aquifers. Significant progress has been made in several areas of research including: (1) delineation of the relative roles and mechanistic function of clays and organic matter in the retention and transformations of pesticides and related organic contaminants by soils, (2) determining the effects of sorption by soil on the bioavailability of pesticides to mammalian (mouse) model and (3) evaluating the in-situ formation of dioxins on soil clays, including the most toxic species, i.e., 2,3,7,8-TCDD. We will continue with these objectives.

Impacts
What was accomplished under these goals? Consideration of soil organic matter and clays as sorptive phases for pesticides in soils will allow development of better pesticide fate and transport models. Polychlorinated dioxins, especially octachlorodioxin and the highly toxic 2,3,7,8- tetrachlorodioxin, are found at inexplicably high levels even in "pristine" rural and agricultural soils, but their origins are unknown. The potential for clay-mediated in-situ formation of dioxins has important implications for past, present and future contamination of rural soils. Dr. Boyd has been designated "Highly Cited Researcher" in the category of Environmental Science by the Institute for Scientific Information (ISI). This is based on literature citations of Dr. Boyd's published work by other researchers in their subsequently published papers. The Highly Cited Researcher designation is given to less than onehalf of one percent of all publishing authors. It is accepted as the "gold standard" for objectively measuring research impact.

Publications

  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Ding, Y., B. J. Teppen, S.A. Boyd, H. Li. 2013. Measurement of assocations between pharmaceuticals and dissolved humic substances using solid phase extraction. Chemosphere 91:314-319. Chen, W.R., C. Liu, S.A. Boyd, B.J. Teppen and H. Li. 2013. Reduction of carbodox mediated by reaction of Mn(III) with oxalic acid. Environ. Sci. Technol. 47:1357-1364.


Progress 01/01/12 to 12/31/12

Outputs
OUTPUTS: The overall objective of this project is to evaluate the transport, transformations and bioavailability of organic contaminants and pesticides in soils, sediments and aquifers. Significant progress has been made in several areas of research including: (1) delineation of the relative roles and mechanistic function of clays and organic matter in the retention and transformations of pesticides and related organic contaminants by soils, (2) determining the effects of sorption by soil on the bioavailability of pesticides to mammalian (mouse) model and (3) evaluating the in-situ formation of dioxins on soil clays, including the most toxic species, i.e., 2,3,7,8-TCDD. PARTICIPANTS: Collaborators include faculty at Michigan State University in the Departments of Chemistry and Civil and Environmental Engineering, Purdue University, Iowa State University/USDA National Soil Tilth Laboratory and Rutgers University. Professional development and training was provided for graduate students and post-doctoral research associates in these programs. TARGET AUDIENCES: Target audience is other researchers in the same or ancillary fields of study. Designation as "Highly Cited Author" demonstrates the high degree to which this audience is being reached. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Consideration of soil organic matter and clays as sorptive phases for pesticides in soils will allow development of better pesticide fate and transport models. Polychlorinated dioxins, especially octachlorodioxin and the highly toxic 2,3,7,8-tetrachlorodioxin, are found at inexplicably high levels even in "pristine" rural and agricultural soils, but their origins are unknown. The potential for clay-mediated in-situ formation of dioxins has important implications for past, present and future contamination of rural soils. Dr. Boyd has been designated "Highly Cited Researcher" in the category of Environmental Science by the Institute for Scientific Information (ISI). This is based on literature citations of Dr. Boyd's published work by other researchers in their subsequently published papers. The Highly Cited Researcher designation is given to less than one-half of one percent of all publishing authors. It is accepted as the "gold standard" for objectively measuring research impact.

Publications

  • Kai Yu, Shaogui Yang, Cun Liu, Hongzhe Chen, Hui Li, Cheng Sun, Stephen A. Boyd. 2012. Degradation of organic dyes via bismuth silver oxide initiated direct oxidation coupled with sodium bismuthate based visible light photocatalysis. Environmental Science and Technology 46:7318-7326.
  • Cuiping Wang, Brian J. Teppen, Stephen A. Boyd, and Hui Li. 2012. Sorption of Lincomycin at Low Concentrations from Water by Soils. Soil Science Society of America Journal 76:1222-1228.
  • Kai Yu, Cheng Gu, Stephen A. Boyd, Cun Liu, Cheng Sun, Brian J. Teppen, and Hui Li. 2012. Rapid and Extensive Debrominatin of Decabromodiphenyl Ether by Smectite Clay-Templated Subnanoscale Zero-Valent Iron. Environmental Science and Technology 46:8969-8975.


Progress 01/01/11 to 12/31/11

Outputs
OUTPUTS: The overall objective of this project is to evaluate the transport, transformations and bioavailability of organic contaminants and pesticides in soils, sediments and aquifers. Significant progress has been made in several areas of research including: (1) delineation of the relative roles and mechanistic function of clays and organic matter in the retention and transformations of pesticides and related organic contaminants by soils, (2) determining the effects of sorption by soil on the bioavailability of pesticides to mammalian (mouse) model and (3) evaluating the in-situ formation of dioxins on soil clays, including the most toxic species, i.e., 2,3,7,8-TCDD. PARTICIPANTS: Collaborators include faculty at Michigan State University in the Departments of Chemistry and Civil and Environmental Engineering, Purdue University, Iowa State University/USDA National Soil Tilth Laboratory and Rutgers University. Professional development and training was provided for graduate students and post-doctoral research associates in these programs. TARGET AUDIENCES: Target audience is other researchers in the same or ancillary fields of study. Designation as "Highly Cited Author" demonstrates the high degree to which this audience is being reached. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Consideration of soil organic matter and clays as sorptive phases for pesticides in soils will allow development of better pesticide fate and transport models. Polychlorinated dioxins, especially octachlorodioxin and the highly toxic 2,3,7,8-tetrachlorodioxin, are found at inexplicably high levels even in "pristine" rural and agricultural soils, but their origins are unknown. The potential for clay-mediated in-situ formation of dioxins has important implications for past, present and future contamination of rural soils. Dr. Boyd has been designated "Highly Cited Researcher" in the category of Environmental Science by the Institute for Scientific Information (ISI). This is based on literature citations of Dr. Boyd's published work by other researchers in their subsequently published papers. The Highly Cited Researcher designation is given to less than one-half of one percent of all publishing authors. It is accepted as the "gold standard" for objectively measuring research impact.

Publications

  • Boyd, Stephen A., Cliff T. Johnston, David A. Laird, Brian J. Teppen, and Hui Li. 2011. Comprehensive Study of Organic Contaminant Adsorption by Clays: Methodologies, Mechanisms and Environmental Implications. In Volume 3: Biophysico-Chemical Processes of Anthropogenic Organic Compounds in Environmental Systems. Edited by Baoshan Xing, Nicola Senesi, and P. Ming Huang, Chapter 2, 51-71 pp. John Wiley, New York, NY.
  • Jia, Hanzhong, Cheng Gu, Stephen A. Boyd, Brian J. Teppen, Cliff T. Johnston, Cunyi Song, and Hui Li. 2011. Comparison of Reactivity of Nanosized Zero-Valent Iron on Clay Surfaces. Soil Science Society of America Journal, 75:357-364.
  • Kaplan, B.L.F., R.B. Crawford, N. Kovalova, A. Arencibia, S.-S. Kim, T.J. Pinnavaia, S.A. Boyd, B.J. Teppen, and N.E. Kaminsky. 2011. TCDD adsorbed on silica as a model for TCDD-contaminated soils: Evidence for suppression of humoral immunity in mice. Toxicology, 282:82-87.
  • Boyd, S.A., C.T. Johnston, T.J. Pinnavaia, N.E. Kaminski, B.J. Teppen, H. Li, B. Khan, R.B. Crawford, N. Kovalova, S.-S. Kim, H. Shao, C. Gu, and B.L. F. Kaplan. 2011. Suppression of humoral immune responses by 2,3,7,8-tetachlorodibenzo-p-dioxin intercalated in smectite clay. Environmental Toxicology Chemistry, 30:2748-2755.
  • Li, H., Cheng Gu, and Stephen A. Boyd. 2011. Synthesis of Clay-Templated Subnano-Sized Zero-Valent Iron (ZVI) Particles, Clay Containing Same, and Use of Same in Contaminant Treatments, Provisional Patent Application (TEC 2009-0132, serial number 61/256,138).


Progress 01/01/10 to 12/31/10

Outputs
OUTPUTS: The overall objective of this project is to evaluate the transport, transformations and bioavailability of organic contaminants and pesticides in soils, sediments and aquifers. Significant progress has been made in several areas of research including: (1) delineation of the relative roles and mechanistic function of clays and organic matter in the retention and transformations of pesticides and related organic contaminants by soils, (2) determining the effects of sorption by soil on the bioavailability of pesticides to mammalian (mouse) model and (3) evaluating the in-situ formation of dioxins on soil clays, including the most toxic species, i.e., 2,3,7,8-TCDD. PARTICIPANTS: Collaborators include faculty at Michigan State University in the Departments of Chemistry and Civil and Environmental Engineering, Purdue University, Iowa State University/USDA National Soil Tilth Laboratory and Rutgers University. Professional development and training was provided for graduate students and post-doctoral research associates in these programs. TARGET AUDIENCES: Target audience is other researchers in the same or ancillary fields of study. Designation as "Highly Cited Author" demonstrates the high degree to which this audience is being reached. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Consideration of soil organic matter and clays as sorptive phases for pesticides in soils will allow development of better pesticide fate and transport models. Polychlorinated dioxins, especially octachlorodioxin and the highly toxic 2,3,7,8-tetrachlorodioxin, are found at inexplicably high levels even in "pristine" rural and agricultural soils, but their origins are unknown. The potential for clay-mediated in-situ formation of dioxins has important implications for past, present and future contamination of rural soils. Dr. Boyd has been designated "Highly Cited Researcher" in the category of Environmental Science by the Institute for Scientific Information (ISI). This is based on literature citations of Dr. Boyd's published work by other researchers in their subsequently published papers. The Highly Cited Researcher designation is given to less than one-half of one percent of all publishing authors. It is accepted as the "gold standard" for objectively measuring research impact.

Publications

  • Li, H., Cheng Gu, and Stephen A. Boyd. 2009. Synthesis of Clay-Templated Subnano-Sized Zero-Valent Iron (ZVI) Particles, Clay Containing Same, and Use of Same in Contaminant Treatments, Provisional Patent Application (TEC 2009-0132, serial number 61/256,138).
  • Gu, Cheng, Hanzhang Jia, Hui Li, Brian J. Teppen, and Stephen A. Boyd. 2010. Highly Reactive Subnano-Sized Zero-Valent Iron Synthesized on Smectite Clay Templates. Environmental Science and Technology, 44:4258-4263.
  • Boyd, Stephen A., Cliff T. Johnston, David A. Laird, Brian J. Teppen, and Hui Li. 2010. Comprehensive Study of Organic Contaminant Adsorption by Clays: Methodologies, Mechanisms and Environmental Implications. In Volume 3: Biophysico-Chemical Processes of Anthropogenic Organic Compounds in Environmental Systems. Edited by Baoshan Xing, Nicola Senesi, and P. Ming Huang (in press).
  • Jia, Hanzhong, Cheng Gu, Stephen A. Boyd, Brian J. Teppen, Cliff T. Johnston, Cunyi Song, and Hui Li. 2010. Comparison of Reactivity of Nanosized Zero-Valent Iron on Clay Surfaces. Soil Science Society of America Journal, doi:10.2136/sssaj2010.0080nps (in the issue of January 2011).


Progress 01/01/09 to 12/31/09

Outputs
OUTPUTS: The overall objective of this project is to evaluate the transport and transformations of organic contaminants and pesticides in soils, sediments and aquifers. Significant progress has been made in several areas of research including: (1) delineation of the relative roles and mechanistic function of clays and organic matter in the retention and transformations of pesticides and related organic contaminants by soils, (2) determining the effects of sorption by soil on the bioavailability of pesticides to degradative bacteria and (3) evaluating the in-situ formation of dioxins on soil clays. PARTICIPANTS: Collaborators include faculty at MSU in the Departments of Chemistry and Civil and Environmental Engineering, Purdue University, Iowa State University/USDA National Soil Tilth Laboratory and Rutgers University. Professional development and training was provided for graduate students and post-doctoral research associates in these programs. TARGET AUDIENCES: Target audience is other researchers in the same or ancillary fields of study. Designation as "Highly Cited Author" demonstrates the high degree to which this audience is being reached. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Consideration of soil organic matter and clays as sorptive phases for pesticides in soils will allow development of better pesticide fate and transport models. Polychlorinated dioxins, especially octachlorodioxin, are found at inexplicably high levels even in "pristine" rural and agricultural soils, but their origins are unknown. The potential for clay-facilitated in-situ formation of dioxins has important implications for past, present and future contamination of rural soils. Dr. Boyd has been designated "Highly Cited Researcher" in the category of Environmental Science by the Institute for Scientific Information (ISI). This is based on literature citations of Dr. Boyd's published work by other researchers in their subsequently published papers. The Highly Cited Researcher designation is given to less than one-half of one percent of all publishing authors. It is accepted as the "gold standard" for objectively measuring research impact.

Publications

  • Wang, Cuiping, Yunjie Ding, Brian J. Teppen, Stephen A. Boyd, and Hui Li. 2009. Role of Interlayer Hydration in Lincomycin Sorption by Smectite Clays. Environmental Science and Technology, 43:6171-6176.
  • Rana, Kiran, Stephen A. Boyd, Brian J. Teppen, Hui Li, Cun Liu, and Cliff T. Johnston. 2009. Probing the Microscopic Hydrophobicity of Smectite Surfaces. A Vibrational Spectroscopic Study of Dibenzo-p-dioxin Sorption to Smectite. Physical Chemistry Chemical Physics, 11: 2976-2985.
  • Liu, Cun, Hui Li, Brian J. Teppen, Cliff T. Johnston, and Stephen A. Boyd. 2009. Mechanisms Associated with the High Adsorption of Dibenzo-p-dioxin from Water by Smectite Clays. Environmental Science and Technology, 43:2777-2783.


Progress 01/01/08 to 12/31/08

Outputs
OUTPUTS: The overall objective of this project is to evaluate the transport and transformations of organic contaminants and pesticides in soils, sediments and aquifers. Significant progress has been made in several areas of research including: (1) delineation of the relative roles and mechanistic function of clays and organic matter in the retention and transformations of pesticides and related organic contaminants by soils, (2) determining the effects of sorption by soil on the bioavailability of pesticides to degradative bacteria and (3) evaluating the in-situ formation of dioxins on soil clays. PARTICIPANTS: Collaborators include faculty at MSU in the Departments of Chemistry and Civil and Environmental Engineering, Purdue University, Iowa State University/USDA National Soil Tilth Laboratory and Rutgers University. Professional development and training was provided for graduate students and post-doctoral research associates in these programs. TARGET AUDIENCES: Target audience is other researchers in the same or ancillary fields of study. Designation as "Highly Cited Author" demonstrates the high degree to which this audience is being reached. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Consideration of soil organic matter and clays as sorptive phases for pesticides in soils will allow development of better pesticide fate and transport models. Polychlorinated dioxins, especially octachlorodioxin, are found at inexplicably high levels even in "pristine" rural and agricultural soils, but their origins are unknown. The potential for clay-facilitated in-situ formation of dioxins has important implications for past, present and future contamination of rural soils. Dr. Boyd has been designated "Highly Cited Researcher" in the category of Environmental Science by the Institute for Scientific Information (ISI). This is based on literature citations of Dr. Boyd's published work by other researchers in their subsequently published papers. The Highly Cited Researcher designation is given to less than one-half of one percent of all publishing authors. It is accepted as the "gold standard" for objectively measuring research impact.

Publications

  • Pereira, T.R., D.A. Laird, M.L. Thompson, C.T. Johnston, B.J. Teppen, H. Li and S.A. Boyd. 2008. Role of smectite quasicrystals on adsorption of dinitrophenol from aqueous suspension as revealed by novel XRD techniques. Soil Sci. Soc. Amer. J., 72:347-354.
  • Charles, S.M., B.J. Teppen, H. Li and S.A. Boyd. 2008. Fractional availability of smectite surfaces in soils for adsorption of nitroaromatic compounds in relation to soil and sediment properties. Soil Sci. Soc. Amer. J., 72:586-594.
  • Feng, Y. and S.A. Boyd. 2008. Bioavailability of soil-sorbed pesticides and organic contaminants. In Q. Huang, P.M. Huang and A. Violante (Eds.) Soil Mineral-Organic Matter-Microorganisms Interactions: Theories and Applications. Springer Publishing Co., New York, NY. pp. 259-279.
  • Gu, Cheng, H. Li, B.J. Teppen and S.A. Boyd. 2008. Octachlorodibenzodioxin formation on Fe(III)-montmorillonite clay. Environ. Sci. Technol., 42:4758-4763.


Progress 01/01/07 to 12/31/07

Outputs
OUTPUTS: The overall objective of this project is to evaluate the transport and transformations of organic contaminants and pesticides in soils, sediments and aquifers. Significant progress has been made in several areas of research including: (1) deliniation of the relative roles and mechanistic function of clays and organic matter in the retention and transformations of pesticides and related organic contaminants by soils, (2) determining the effects of sorption by soil on the bioavailability of pesticides to degradative bacteria and (3) assessing the occurrence of historic pesticide contamination of agricultural soils and toxicity implications as these soils change from farms to other uses. PARTICIPANTS: Collaborators include faculty at MSU in the departments of Chemistry and Civil and Environmental Engineering, Purdue University, Iowa State University/USDA National Soil Tilth Laboratory and Rutgers University. Professional development and training was provided for graduate students and post-doctoral research associates in these programs. TARGET AUDIENCES: Target audience is other researchers in the same or ancillary fields of study. Designation as "Highly Cited Author" demonstrates the high degree to which this audience is being reached.

Impacts
Consideration of soil organic matter and clays as sorptive phases for pesticides in soils will allow development of better pesticide fate and transport models. There is a need to consider historic pesticide contamination as agricultural land changes from farms to other uses. The primary concern has to do with human health impacts of these residues (e.g., DDX, Dieldrin, Pb, As) resulting from ingestion of contaminated soil, especially by children. Dr. Boyd has been designated "Highly Cited Researcher" in the category of Environmental Science by the Institute for Scientific Information (ISI). This is based on literature citations of Dr. Boyd's published work by other researchers in their subsequently published papers. The Highly Cited Researcher designation is given to less than one-half of one percent of all publishing authors. It is accepted as the "gold standard" for objectively measuring research impact.

Publications

  • Roberts, M.G., C.L. Rugh, H. Li, B.J. Teppen and S.A. Boyd. 2007. Reducing bioavailability and phytotoxicity of 2,4-dinitrotoluene by sorption on K-smectite clay. Environ. Toxicol. Chem., 26:358-360.
  • Li, H., T.R. Pereira, B.J. Teppen, D.A. Laird, C.T. Johnston and S.A. Boyd. 2007. Ionic strength-induced formation of smectite quasicrystals enhances nitroaromatic compound adsorption. Environ. Sci. Technol., 41:1251-1256.
  • Roberts, M.G., C.L. Rugh, H. Li, B.J. Teppen and S.A. Boyd. 2007. Geochemical modulation of bioavailability and toxicity of nitoaromatic compounds to aquatic plants. Environ. Sci. Technol., 41:1641-1645.
  • Pereira, T.R., D.A. Laird, M.L. Thompson, C.T. Johnston, B.J. Teppen, H. Li and S.A. Boyd. 200_. A comparison XRD study of dinitrophenol sorption on smectites in aqueous suspensions and smectite films at varying pH. Soil Sci. Soc. Amer. J., accepted.
  • Tsuneta, T., M. Hanna, C. Grindatti, J.F. Quensen, S.A. Boyd and R. Loch Caruso. 200_. Stimulatory effects of a microbially dechlorinated polychlorinated biphenyl (PCB) mixture on rat uterine contraction. Environ. Res., accepted.


Progress 01/01/06 to 12/31/06

Outputs
The overall objective of this project is to evaluate the transport and transformations of organic contaminants and pesticides in soils, sediments and aquifers. Significant progress has been made in several areas of research including: (1) deliniation of the relative roles and mechanistic function of clays and organic matter in the retention and transformations of pesticides and related organic contaminants by soils, (2) determining the effects of sorption by soil on the bioavailability of pesticides to degradative bacteria and (3) assessing the occurrence of historic pesticide contamination of agricultural soils and toxicity implications as these soils change from farms to other uses.

Impacts
Consideration of soil organic matter and clays as sorptive phases for pesticides in soils will allow development of better pesticide fate and transport models. There is a need to consider historic pesticide contamination as agricultural land changes from farms to other uses. The primary concern has to do with human health impacts of these residues (e.g., DDX, Dieldrin, Pb, As) resulting from ingestion of contaminated soil, especially by children.

Publications

  • Vaggarwal, V., H. Li, S.A. Boyd and B.J. Teppen. 2006. Enhanced sorption of trichloroethylene by smectite clay exchanged with Cs+. Environ. Sci. Technol., 40:894-899.
  • Roberts, M.G., H. Li, B.J. Teppen and S.A. Boyd. 2006. Sorption of nitroaromatics by ammonium- and organic ammonium-exchanged smectite shifts from surface adsorption to a partition-dominated process. Clays Clay Miner., 54:426-434.
  • Charles, S.M., B.J. Teppen, H. Li, D.A. Laird and S.A. Boyd. 2006. Exchangeable cation hydration properties strongly influence soil sorption of nitroaromatic compounds. Soil Sci. Soc. Amer. J., 70:1470-1479.
  • Li, H., B.J. Teppen, D.A. Laird, C.T. Johnson and S.A. Boyd. 2006. Effects of increasing potassium chloride and calcium chloride ionic strength on pesticide sorption by potassium- and calcium-smectite. Soil Sci. Soc. Amer. J., 70:1889-1895.
  • Park, J.H., M. Sharer, Y. Feng, S.Y. Chung, T.C. Voice and S.A. Boyd. 2006. Effects of aging on the bioavailability and sorption/desorption behavior of biphenyl in soils. Water Sci. Technol. 52:95-105.
  • Charles, S.M., H. Li, B.J. Teppen and S.A. Boyd. 2006. Quantifying the availability of clay surfaces in soils for adsorption of nitrocyanobenzene and diuron. Environ. Sci. Technol., 40:7751-7756.
  • Gellner, J.W., X. Zhao, M. Gir, S.A. Boyd and T.C. Voice. 2006. Hydraulic conductivity of soil sorptive zones created by in-situ injection of a cationic surfactant. J. Environ. Eng., 132:1659-1663.


Progress 01/01/05 to 12/31/05

Outputs
The overall objective of this project is to evaluate the transport and transformations of organic contaminants and pesticides in soils, sediments and aquifers. Significant progress has been made in several areas of research including: (1) deliniation of the relative roles and mechanistic function of clays and organic matter in the retention of pesticides by soils, (2) determining the effects of sorption by soil on the bioavailability of pesticides to degradative bacteria and (3) assessing the occurrence of historic pesticide contamination of agricultural soils and toxicity implications as these soils change from farms to other uses.

Impacts
Consideration of soil organic matter and clays as sorptive phases for pesticides in soils will allow development of better pesticide fate and transport models. There is a need to consider historic pesticide contamination as agricultural land changes from farms to other uses. The primary concern has to do with human health impacts of these residues (e.g., DDX, Dieldrin, Pb, As) resulting from ingestion of contaminated soil, especially by children.

Publications

  • Chapelle, M.A., D.A. Laird, M.L. Thompson, H. Li, B.J. Teppen, C.T. Johnston and S.A. Boyd. 2005. Influence of smectite hydration and swelling on atrazine sorption affinity. Environ. Sci. Technol., 39:3150-3156.
  • Ganey, P.E. and S.A. Boyd. 2005. An approach to evaluation of the effect of bioremediation on biological activity of environmental contaminants: Dechlorination of polychlorinated biphenyls. Environ. Health Perspect, 113:180-185.
  • Arroyo, L.J., H. Li, B.J. Teppen and S.A. Boyd. 2005. A simple method for partial purification of reference clays. Clays and Clay Miner., 53:511-519.
  • deOliveria, M.F., C.T. Johnston, G.S. Premachandra, B.J. Teppen, H. Li, D.A. Laird, D. Zhu and S.A. Boyd. 2005. Spectroscopic studies of carbaryl sorption on smectite from aqueous suspension. Environ. Sci. Technol., 39:9123-9129.
  • Arroyo, L.J., H. Li, B.J. Teppen, C.T. Johnston and S.A. Boyd. 2005. Reduction of structural Fe3+ in smectite coupled to oxidation of 1-naphthol. Clays Clay Miner., 53:587-596.


Progress 01/01/04 to 12/31/04

Outputs
The overall objective of this project is to evaluate the transport and transformations of organic contaminants and pesticides in soils, sediments and aquifers. Significant progress has been made in several areas of research including: (1) deliniation of the relative roles and mechanistic function of clays and organic matter in the retention of pesticides by soils, (2) determining the effects of sorption by soil on the bioavailability of pesticides to degradative bacteria and (3) assessing the occurrence of historic pesticide contamination of agricultural soils and toxicity implications as these soils change from farms to other uses.

Impacts
Consideration of soil organic matter and clays as sorptive phases for pesticides in soils will allow development of better pesticide fate and transport models. There is a need to consider historic pesticide contamination as agricultural land changes from farms to other uses. The primary concern has to do with human health impacts of these residues (e.g., DDX, Dieldrin, Pb, As) resulting from ingestion of contaminated soil, especially by children.

Publications

  • Johnston, C.T., S.A. Boyd, B.J. Teppen and G. Sheng. 2004. Sorption of nitroaromatic compounds on clay surfaces. In S.A. Auerbach, K.A. Carrado, P.K. Satta (Eds.). Handbook of Layered Materials Science and Technology. Marcel Dekker, New York, NY, pp. 155-189.
  • Li, H., B.J. Teppen, C.T. Johnston and S.A. Boyd. 2004. Thermodynamics of nitroaromatic compound adsorption from water by smectite clay. Environ. Sci. Technol., 38:5433-5442.
  • Li, H., B.J. Teppen, D.A. Laird, C.T. Johnston and S.A. Boyd. 2004. Geochemical modulation of pesticide sorption by smectite clay. Environ. Sci. Technol., 38:5383-5399.
  • Park, J.-H., Y. Feng, T.C. Voice and S.A. Boyd. 2004. Sorbed atrazine shifts to non-desorbable sites of soil organic matter during aging. Water Res., 38:3881-3892.
  • Arroyo, L.J., H. Li, B.J. Teppen and S.A. Boyd. 2004. Hydrolysis of carbaryl by carbonate impurities in reference clay SWy2. J. Agric. Food Chem., 52:8066-8073.


Progress 01/01/03 to 12/31/03

Outputs
The overall objective of this project is to evaluate the transport and transformations of organic contaminants and pesticides in soils, sediments and aquifers. Significant progress has been made in several areas of research including: (1) deliniation of the relative roles and mechanistic function of clays and organic matter in the retention of pesticides by soils, (2) determining the effects of sorption by soil on the bioavailability of pesticides to degradative bacteria and (3) assessing the occurrence of historic pesticide contamination of agricultural soils and toxicity implications as these soils change from farms to other uses.

Impacts
Consideration of soil organic matter and clays as sorptive phases for pesticides in soils will allow development of better pesticide fate and transport models. There is a need to consider historic pesticide contamination as agricultural land changes from farms to other uses. The primary concern has to do with human health impacts of these residues (e.g., DDX, Dieldrin, Pb, As) resulting from ingestion of contaminated soil, especially by children.

Publications

  • Li, H., G. Sheng, B.J. Teppen, C.T. Johnston and S.A. Boyd. 2003. Sorption and desorption of pesticides by clay minerals and humic acid-clay complexes. Soil Sci. Soc. Amer. J. 67:122-131.
  • Chun, Y., G. Sheng and S.A. Boyd. 2003. Sorptive characteristics of tetraalkylammonium-exchanged smectite clays. Clays Clay Miner. 51:416-421.
  • Sharer, M., J.-H. Park, T.C. Voice and S.A. Boyd. 2003. Aging effects on the sorption/desorption characteristics of anthropogenic organic compounds in soils. J. Environ. Qual. 32:1385-1392.
  • Sharer, M., J.H. Park, T.C. Voice and S.A. Boyd. 2003. Time dependence of chlorobenzene sorption/desorption by soils. Soil Sci. Soc. Amer. J. 67:1740-1745.


Progress 01/01/02 to 12/31/02

Outputs
The overall objective of this project is to evaluate the transport and transformations of organic contaminants and pesticides in soils, sediments and aquifers. Significant progress has been made in several areas of research including: (1) deliniation of the relative roles and mechanistic function of clays and organic matter in the retention of pesticides by soils, (2) determining the effects of sorption by soil on the bioavailability of pesticides to degradative bacteria and (3) elucidating changes in toxicities of PCBs that result from microbial dechlorination.

Impacts
Consideration of soil organic matter and clays as sorptive phases for pesticides in soils will allow development of better pesticide fate and transport models. Impact of organo-clays developed under this project have potential application as barrier components for the isolation of hazardous waste and provide the basis for an in-situ technology to immobilize contaminant plumes in the subsurface. Dechlorination of PCBs can reduce their toxicities and hence the risks they pose to human health.

Publications

  • Sheng, G., C.T. Johnston, B.J. Teppen and S.A. Boyd. 2002. Adsorption of dinitrophenol herbicides from water by Montmorillonites. Clays Clay Miner. 50:25-34.
  • Johnston, C.T., G. Sheng, B.J. Teppen, S.A. Boyd and M.F. deOliveria. 2002. Spectroscopic study of dinitrophenol herbicide sorption on smectite. Environ. Sci. Technol. 36:5067-5074.


Progress 01/01/01 to 12/31/01

Outputs
The overall objective of this project is to evaluate the transport and transformations of organic contaminants and pesticides in soils, sediments and aquifers. Significant progress has been made in several areas of research including: (1) deliniation of the relative roles and mechanistic function of clays and organic matter in the retention of pesticides by soils, (2) determining the effects of sorption by soil on the bioavailability of pesticides to degradative bacteria and (3) elucidating changes in toxicities of PCBs that result from microbial dechlorination.

Impacts
Consideration of soil organic matter and clays as sorptive phases for pesticides in soils will allow development of better pesticide fate and transport models. Impact of organo-clays developed under this project have potential application as barrier components for the isolation of hazardous waste and provide the basis for an in-situ technology to immobilize contaminant plumes in the subsurface. Dechlorination of PCBs can reduce their toxicities and hence the risks they pose to human health.

Publications

  • Bae, J., M.M. Mouse, J.F. Quensen, S.A. Boyd and R. Loch-Caruso. 2001. Stimulation of contraction of pregnant rat uterus in vitro by non-dechlorinated and microbially dechlorinated mixtures of polychlorinated biphenyls. Environ. Health Perspect. 109:275-282.
  • Sheng, G., C.T. Johnston, B.J. Teppen and S.A. Boyd. 2001. Potential contributions of smectite clays and organic matter to pesticide retention in soils. J. Agric. Food Chem. 49:2899-2907.
  • Rakhshandehroo, G.R., R.B. Wallace, X. Zhao, S.A. Boyd and T.C. Voice. 2001. Hydraulic conductivities of surfactant-enhanced sorbent zone soils. J. Environ. Eng., 127:724-729.


Progress 01/01/00 to 12/31/00

Outputs
The overall objective of this project is to evaluate the transport and transformations of organic contaminants and pesticides in soils, sediments and aquifers. Significant progress has been made in several areas of research including: (1) deliniation of the relative roles and mechanistic function of clays and organic matter in the retention of pesticides by soils, (2) determining the effects of sorption by soil on the bioavailability of pesticides to degradative bacteria and (3) elucidating changes in toxicities of PCBs that result from microbial dechlorination.

Impacts
Consideration of soil organic matter and clays as sorptive phases for pesticides in soils will allow development of better pesticide fate and transport models. Impact organo-clays developed under this project have potential application as barrier components for the isolation of hazardous waste and provide the basis for an in-situ technology to immobilize contaminant plumes in the subsurface. Dechlorination of PCBs can reduce their toxicities and hence the risks they pose to human health.

Publications

  • Sheng, G. and S.A. Boyd. 2000. Polarity effect on dichlorobenzene sorption by hexadecyltrimethylammonium-clays. Clays and Clay Minerals 48:43-50.
  • Ganey, P.E., J.F. Quensen, M.A. Mousa, S.A. Boyd, M.A. Wagner and L.J. Fischer. 2000. Biological activity associated with noncoplanar PCBs after microbial dechlorination of Aroclor 1242 and Aroclor 1254. Environ. Toxicol. Chem. 19:1311-1316.
  • Chiou, C.T., D.E. Kile, D.W. Rutherford, G. Sheng and S.A. Boyd. 2000. Sorption of selected organic compounds from water to a peat soil and its humic-acid and humin fractions: potential sources of the sorption nonlinearity. Environ. Sci. Technol. 34:1254-1258.
  • Feng, Y., J.-H. Park, T.C. Voice and S.A. Boyd. 2000. Bioavailability of soil-sorbed biphenyl to bacteria. Environ. Sci. Technol. 34:1977-1984.


Progress 01/01/99 to 12/31/99

Outputs
The overall objective of this project is to evaluate the transport and transformations of organic contaminants and pesticides in soils, sediments and aquifers. Significant progress has been made in several areas of research including: (1) development and evaluation of organo-modified-clays for immobilization of organic contaminants and metals, (2) reductive dechlorination of PCBs by anaerobic bacteria found in sediments, (3) effect of residual petroleum contamination on bioavailability and biodegradation of PCBs, and (4) use of commercial surfactants to control the immobilization of organic contaminants in soils.

Impacts
Impact organo-clays developed under this project have potential application as barrier components for the isolation of hazardous waste and provide the basis for an in-situ technology to immobilize contaminant plumes in the subsurface. Dechlorination of PCBs can reduce their toxicities and hence the risks they pose to human health.

Publications

  • Ye, D., J.F. Quensen, J.M. Tiedje and S.A. Boyd. 1999. 2-Bromoethanesulfonate, sulfate, molybdate, and ethanesulfonate inhibit anaerobic dechlorination of polychlorobiphenyls by pasturized microorganisms. Appl. Environ. Microbiol. 65:327-329.
  • Sheng, G., S. Xu and S.A. Boyd. 1999. A dual function organoclay sorbent for lead and chlorobenzene. Soil Sci. Soc. Amer. J. 63:73-78.
  • Park, J.W. and S.A. Boyd. 1999. Sorption of chlorobiphenyls in sediment-water systems containing nonionic surfactants. J. Environ. Qual. 28:945-952.
  • Boyd, S.A. and G. Sheng. 1999. Contaminant plume management utilising in situ organoclay sorbent zones. In P. Misaelides et al. (Eds.) Natural Microporous Materials in Environmental Technology. Kluwer Academic Publishers, Netherlands, pp. 71-83.
  • Zwiernik, M.J., J.F. Quensen and S.A. Boyd. 1999. Residual petroleum in sediments reduces the bioavailability and rate of reductive dechlorination of Aroclor 1242. Environ. Sci. Technol. 33:3574-3578.


Progress 01/01/98 to 12/31/98

Outputs
The overall objective of this project is to evaluate the transport and transformations of organic contaminants and pesticides in soils, sediments and aquifers. Significant progress has been made in several areas of research including: (1) understanding mechanistic interactions of organic contaminants with organo-modified clays used to reduce transport potential, (2) stimulation of anaerobic microbial reductive dechlorination of PCB utilizing iron sulfate amendments, (3) evaluating the effect of sorption on availability of contaminants to bacteria for biodegradation, and (4) assessing alterations in the toxicity of commercial PCB mixtures (Aroclors) that have undergone microbial transformations.

Impacts
(N/A)

Publications

  • Zwiernik, M.J., J.F. Quensen and S.A. Boyd. 1998. Iron sulfate amendments stimulate extensive anaerobic PCB dechlorination. Environ. Sci. Technol., 21:3360-3365.
  • Mousa, M.A., P.E. Ganey, J.F. Quensen, B.V. Mudhukar, K.Chou, J.P. Giesy, L.J. Fischer and S.A. Boyd. 1998. Altered biological activities of commercial PCB mixtures after microbial reductive dechlorination. Environ. Health Perspect., 106:1263-1270.
  • Boyd, S.A. and R. Kukkadapu. 1998 Organophilic quaternary phosphonium ion-exchanged smectite clays. U.S. Patent No. 5,747,403.
  • Quensen, J.F., M.A. Mousa, S.A. boyd, J.T. Sanderson, K.L. Fruese and J.P. Giesy. 1998. Reduction in Ah receptor mediated activity of PCB mixtures due to anaerobic microbial dechlorination. Environ. Toxicol. Chem., 17:806-813.
  • Rakkshandehrou, G.R., R.B. Wallace, S.A. Boyd, and T.C. Voice. 1998. Hydraulic characteristics of organomodified soils for use in sorptive zone applications. Soil Sci. Soc. Amer. J. 62:5-12.
  • Sheng, G. and S.A. Boyd. 1998. Relation of water and neutral organic compounds in the interlayers of mixed Ca/trimethylphenylammonium-smectites. Clays and Clay Minerals. 46:10- 17.
  • Sheng, G., X-Wang, S. Wu and S.A. Boyd. 1998. Enhanced sorption of organic contaminants by smectitic soils modified with a cationic surfactant. J. Environ. Qual., 27:806-814.
  • Lawrence, M.A.M., R.K. Kukkadapu and S.A. Boyd. 1998. Adsorption of phenol and chlorophenols by tetramethylammonium-and tetramethylphosphonium-exchanged montmorillonite. Appl. Clay Sci., 13:13-20.


Progress 01/01/97 to 12/31/97

Outputs
The overall objective of this project is to evaluate the movement and degradation of organic contaminants and pesticides in soils and sediments. One area of significant progress is the creation of subsurface sorbent zones for contaminant plume management. This in-situ technology relies on the conversion of native clays into organo-clays which are effective sorbents for common groundwater contaminants. The sorbent zones are created via injections of cationic surfactants, and function to intercept and immobilize contaminant plumes, thereby protecting downgradient water supplies. A second area of progress is understanding how sorption of contaminants influences their availability for biodegradation. Natural and synthetic sorbents manifest differential availability of sorbed compounds; generally bioavailability is lessened by sorption. Similarly, different bacterial strains have differential ability to access sorbed substrate. Lastly, we have begun evaluating changes in the toxicities of commercial PCB mixtures that have undergone microbial reductive dechlorination. Biological activities may increase, decrease or remain unchanged.

Impacts
(N/A)

Publications

  • Patent - Boyd, S.A. and R. Kukkadaupa. 1997. Method of removing organic contaminants from air and water with organophilic, quaternary phosphonium ion-exchanged smectite clays. U.S. Patent No. 5,635,075.
  • Xu, S., G. Sheng and S. A. Boyd. 1997. Use of organoclays in pollution abatement. Adv. Agron. 59: 25-61.
  • Sheng, G. and S. A. Boyd. 1997. Organoclays/soil modification and their use in pollution prevention and environmental remediation. Nature Magz. China 19:95-104.
  • Angus, W. G. R., M. A. Mousa, V. M. Vargas, J. F. Quensen, S. A. Boyd and M. L. Contreras. 1997. Inhibition of L-aromatic amino acid decarboxylase by polychlorinated biphenyls. NeuroToxicology. 18:857-868.
  • Sheng, G., S. Xu and S. A. Boyd. 1997. Surface heterogeneity of trimethylphenylammonium- smectite as revealed by adsorption of aromatic hydrocarbons from water. Clays and Clay Minerals, 45:659-669.


Progress 01/01/96 to 12/30/96

Outputs
The goals of the project are to understand the chemical and biological processesthat determine the fate of organic contaminants and pesticides in soils and sediments, and to develop the scientific basis for new technologies aimed at remediating contaminated soils, sediments and aquifers. Progress has been made in three general areas of research: (1) The influence of sorption on the availability of contaminants for biodegradation. Availability of contaminants for biodegradation may be limited by sorption depending on characteristics of the degradative bacteria and the sorbent, as well as contact time between the contaminant and sorbent. (2) Reductive dechlorination of PCBs. Anaerobic microbial dechlorination of PCBs reduces their toxic effects. (3) Various aspects of the in-situ formation of sorbent zones to intercept and immobilize contaminant plumes have been studied. Patent No. 5, 581,084. 1996. Method of removing hydrocarbon contaminants from air and water with organophilic, quaternary phosphonium ion-exchanged clays.

Impacts
(N/A)

Publications

  • SHENG, G., XU, S., BOYD, S. A. 1996. Mechanisms controlling sorption of neutral organic contaminants by surfactant derived and natural organic matter. Environ. Sci. Technol., 30:1553-1557.
  • MOUSA, M. A., QUENSEN, J. F., CHOU, K., BOYD, S. A. 1996. Microbial dechlorination alleviates inhibitory effects of PCBs on mouse gamete fertilization in-vitro. Environ. Sci. Technol. 30:2087-2092.
  • STEVENS, J. J., ANDERSON, S. J., BOYD, S. A. 1996. FTIR study of competitive water-arene sorption on tetramethylammonium- and trimethylphenylammonium-montmorillonites. Clays and Clay Minerals 44:88- 95.
  • SHENG, G., XU, S., BOYD, S. A. 1996. Cosorption of organic contaminants from water by hexadecyltrimethylammonoium-exchanged clays. Water Res. 30:1483-1489.
  • MOUSA, M., ANGUS, W. G. R., QUENSEN, J. F., III, CONTRERAS, M. L., BOYD, S. A. 1996. Distribution of PCBs in PC12 cell culture system and relationship with thelevels of DNA and dopamine. In Vitro Toxicology, 9:215-221.
  • XU, S., SHENG, G., BOYD, S. A. 1996. Use of organoclays in pollution abatement. Adv. Agron., 59:25-61.
  • CHIBWE, M., UKRAINCZYK, L., BOYD, S., PINNAVAIA, T. 1996. Catalytic properties of biomimetic metallo macrocycles intercalated in layered double hydroxides & smectite clay: The importance of edge-site access. J. Molec. Catal., 113:249-256.


Progress 01/01/95 to 12/30/95

Outputs
The goals of the project are to understand the chemical and biological processesthat determine the fate of organic contaminants and pesticides in soils and sediments, and to develop the scientific basis for new technologies aimed at remediating contaminated soils, sediments and aquifers. Progress has been made in three general areas of research: (1) The influence of sorption on the availability of contaminants for biodegradation. Availability of contaminants for biodegradation may be limited by sorption depending on characteristics of the degradative bacteria and the sorbent, as well as contact time between the contaminant and sorbent. (2) Reductive dechlorination of PCBs. Addition of ferrous iron results in higher rates and extents of dechlorination. (3) Various aspects of the in-situ formation of sorbent zones to intercept and immobilize contaminant plumes have been studied. Patent No. 5,401-418. 1995. Method of removing hydrocarbon contaminants from air and water with organophilic, quaternary ammonium ion-exchanged clays.

Impacts
(N/A)

Publications

  • Xu,S. and Boyd,S. A. 1995. Cationic surfactant sorption to a vermiculitic subsoil via hydrophobic bonding. Environ. Sci. Technol. 29:312-320.
  • Ukrainczyk,L., Chibwe,M., Pinnavaia,T.J., and Boyd, S.A. 1995. Reductive dechlorination of carbon tetrachloride in water catalyzed by mineral supported biomimetic cobalt macrocycles. Environ. Sci. Technol. 29:439-445.
  • Sun,S., Inskeep,W.P. and Boyd,S.A. 1995. Sorption of nonionic organic compounds in soil-water systems containing a micelle forming surfactant. Environ. Sci. Technol. 29:903-913.
  • Ye,D., Quensen,J.F.III, Tiedje,J.M. and Boyd,S.A. 1995. Evidence for para dechlorination of polychlorobiphenyls (PCBs) by methanogenic bacteria. Appl. Environ. Microbiol. 61:2166-2171.
  • Pennell,K.D., Boyd,S.A. and Abriola,L.M. 1995. The surface area of soil organic matte reexamined. Soil Sci. Soc. Amer. J., 59:1012-1018.
  • Xu,S. and Boyd,S.A. 1995. Cationic surfactant adsorption by swelling and non-swelling layer silicates. Langmuir, 11:2508-2514.
  • Crocker,F.H., Guerin,W.F. and Boyd,S.A. 1995. Bioavailability of naphthalene sorbed to cationic surfactant-modified smectite clay. Environ. Sci. Technol. 29:2953-2958.
  • Xu,S. and Boyd,S.A. 1995. An alternative model for cationic surfactant adsorption by layer silicates. Environ. Sci. Technol. 29:3002-3028.


Progress 01/01/94 to 12/30/94

Outputs
The goals of the project are to understand the chemical and biological processesthat determine the fate of organic contaminants and pesticides in soils and sediments, and to develope the scientific basis for new technologies aimed at remediating contaminated soils, sediments and aquifers. Progress has been made in three general areas of research: (1) The influence of sorption on the availability of contaminants for biodegradation. Availability of contaminants for biodegradation may be limited by sorption depending on characteristics of the degradative bacteria and the sorbent, as well as contact time between the contaminant and sorbent. (2) Reductive dechlorination of PCBs. Removal of heavy metals from sediments by extraction, chelation or percipitation may result in higher rates and extents of dechlorination. (3) Various aspects of the in-situ formation of sorbent zones to intercept and immobilize contaminant plumes have been studied.

Impacts
(N/A)

Publications

  • UKRAINCZYK, L., BOYD, S. A., ET AL. 1994. ESR study of Co(II)-tetrakis-(N-methyl-4-pyridiniumyl) porphyrin and Co(II)-tetrasulfo-phthalocyanine intercalated in layered alumininosilicates... J. Phys. Chem. 98:2668-2676.
  • BRIXIE, J. M., BOYD, S. A. 1994. Treatment of contaminated soils with organoclays to reduce leachable pentrachlorophenol. J. Environ. Qual. 23:1283-1280.
  • XU, S., BOYD, S.A. 1994. Cation exchange chemistry of hexadecyltrimethyl-ammonium in subsoils containing vermiculite. Soil Sci. Soc. Amer. J. 58:1382- 1391.
  • BOYD, S. A., JAYNES, W. F. 1994. Role of layer charge in organic contaminant sorption by organoclays, pp 48-77. In A. R.Mermut (ed.) Layer Charge Characteristics of 2:1 Silicate Clay Minerals. CMS Workshop Lecture, Vol. 6.
  • BOYD, S. A. 1994. The chemistry of organic contaminant transport in soils. Cent. Eur. J. Publ. Hlth. 2:56-59.


Progress 01/01/93 to 12/30/93

Outputs
The goals of the project are to understand the chemical and biological processesthat determine the fate of organic contaminants and pesticides in soils and sediments, and to develop new approaches for remediating contaminated soils, sediments and waters. The three areas of research and a summary statement of progress in each follows: (1) The influence of sorption on the availablity of contaminants for biodegradation. We have developed a new kinetic method to study bioavailability of soil-sorbed contaminants which has shown differential availability to individual bacterial species, sorbent specific availabilty and decreased bioavailablity upon prolonged contaminant aging in soils. (2) Reductive dechlorination of PCBs. We are studying factors that may limit reductive dechlorination of PCBs and ways to overcome their limitations. The presence of toxic metals and petroleum co-contaminants as well as the congener specificity of the PCB degrading bacteria are potential limiting factors. Reduced bioavailability due to strong PCB sorption is another limiting factor that may be overcome using surfactants. (3) The creation of an in-situ subsurface sorption zone to intercept on advancing contaminant plume coupled with biodegradation of the immobilized contaminants is being developed as a comprehensive soil remediation technology. Patent No: 5,268,109. Date: Dec. 7, 1993.

Impacts
(N/A)

Publications

  • MORRIS, P.J., QUENSEN, J.F., TIEDJE, J.M., BOYD, S.A. 1993. Reductive dechlorination of commercial polybrominated biphenyl mixture, Firemaster FM-BP6, by anaerobic microorganisms from sediments. Appl.Environ.Micro. 58:3249-3256.
  • GUERIN, W.F., BOYD, S.A. 1993. Bioavailability of soil-sorbed napthalene to bacteria...In: Sorption and degradation of pesticides and organic chemicals in soils (D.W. Linn ed.). Soil. Sci. Soc. Amer. Special Publication No. 32.
  • SUN, S., BOYD, S.A. 1993. Sorption of nonionic organic compounds in soil-water systems containing petroleum sulfonate-oil surfactants. Environ. Sci. Technol. 27:1340-1346.
  • MORRIS, P.J., QUENSEN, J.F., TIEDJE, J.M., BOYD, S.A. 1993. An assessment of reductive debromination of polybrominated biphenyls in the Pine River reservoir (St. Louis, MI). Environ. Sci. Technol. 27:1580-1586.


Progress 01/01/92 to 12/30/92

Outputs
This project focused on sorption, biodegradation and sorption-biodegradation interactions or organic contaminants and pesticides in soils and sediments. Sorption of contaminants appears to decrease their availability for biodegradation, although some bacteria have greater access to soil-bound contaminants. Aging of pesticide residues, e.g. simazine, in field weathered soils appears to further decrease bioavailability. This apparently results from extremely slow desorption kinetics of aged residues, and manifests increased persistence and lowered aqueous phase pesticide concentrations. Petronate surfactants cap be used to substantially increase the aqueous phase concentrations of contaminants in soils, and hence increase their availability for biodegradation. Additional studies were carried out on the degradation of polychlorinated and polybrominated biphenyls (PCBs and PBBs). Anaerobic bacteria from contaminated sediments cadn reductively dehalogenate PCBs and PBBs, resulting in less toxic and less persistent products. The presence of co-contaminants, e.g. petroleum products and heavy metals, may inhibit reductive dehalogenation at certain sites.

Impacts
(N/A)

Publications


    Progress 01/01/91 to 12/30/91

    Outputs
    This project is focused on (1) understanding the movement and degradation of organic contaminants and pesticides in soils and sediments, and (2) developing novel chemical and biological methods for waste detoxification and restoration of contaminated soils, subsoils and sediments. The specific areas of research and progress are summarized below: (1) Organo-clays have been synthesized and characterized as sorbents for pollutant chemicals. They are being developed to improve clay barrier technology, for chemical waste stabilization and for purification of contaminated air and water. (2) Soil modification technology has been discovered to enhance sorption and reduce transport of common groundwater pollutants. This is now being coupled to biodegradation of the immobilized contaminants as a comprehensive soil restoration technology. (3) Basic studies are being conducted on the influence of sorption/desorption processes on the bioavailability (and biodegradability) of soil-bound organic contaminants. Numerous physicochemical (sorption coefficient, desorption rate, sorption mechanism, contaminant aging) and microbiological factors (attachment, mobility, chemtoxis) influence bioavailability. (4) Dechlorination of PCBs by anaerobic microorganisms from sediments has been demonstrated.

    Impacts
    (N/A)

    Publications

    • TIEDJE, J.M., QUENSEN, J.F. III, MOHN, W.W., SCHIMEL, J.P., COLE, J.A. and BOYD, S.A. 1991. "Reductive dechlorination of chlorinated aromatic pollutants." Tn R. W. Rossmoore (Ed.), Biodeterioration and Biodegradation, Elsevier Applied Sci.
    • JAYNES, W.F. and BOYD, S.A. 1991. Clay mineral type and organic compound sorption by hexadecyltrimethylammonium-exchanged clays. Soil Sci. Soc. Amer. J. 55:43-48.
    • BOYD, S.A., JAYNES, W.F. and ROSS, B.S. 1991. "Immobilization of organic contaminants by organo-clays: Application to soil restoration and hazardous waste containment." In R. S. Baker (Ed.) Organic Substances and Sediments in Water, Lewis.
    • SUN, S. and BOYD, S.A. 1991. Sorption of polychlorobiphenyl congeners by residual poly-chlorobiphenyl-oil phases in soils. J. Environ. Qual., 20:557-561. JAYNES, W.F. anD BOYD, S.A. 1991. Hydrophobicity of siloxane surfaces in smectites as revealed by aromatic hydrocarbon adsorption from water. Clays and Clay Minerals, 39:428-436.


    Progress 01/01/90 to 12/30/90

    Outputs
    Research is ongoing in the following areas: (1) bioavailability of soil-bound contaminants, (2) immobilization of organic contaminants by modified soils and clays, (3) reductive dechlorination of polychlorobiphenyls, (4) sorptive interactions of organic contaminants with soil organic matter. Significant research accomplishments this year are summarized below: (1) Demonstrated that soil-bound contaminants are rendered partially or completely unavailable to microbial degraders. (2) Demonstrated that aged Simazine residues in field weathered soil are protected from biodegradation. (3) Developed a new modified clay, trimethylphenylammonium-smectite, that is an effective adsorbent of water-soluble aromatic hydrocarbons constituents of petroleum. (4) Demonstrated the reductive dechlorination of commercial PCB mixtures (Aroclor 1242, Aroclor 1248, Aroclor 1254, Aroclor 1260) by anaerobic bacteria from sediments. (5) Demonstrated that anthropogenic organic phases derived from petroleum or PCB oils act as powerful sorptive sinks for organic contaminants in soils heavily contaminated by oil or PCB mixtures.

    Impacts
    (N/A)

    Publications

    • BOYD, S. A. and S. SUN. 1990. Residual petroleum and PCB oils as sorptive phases for organic contaminants in soil. Environ. Sci. Technol. 24:142-144.
    • LEE, J. F., M. M. MORTLAND, C. T. CHIOU, D. E. KILE and S. A. BOYD. 1990. Adsorption of benzene, toluene and xylene by two tetramethylammonium smectites of different charge densities. Clays and Clay Minerals, 38:113-120.
    • BOYD, S. A. and M. M. MORTLAND. 1990. Enzyme Interactions with Clays and Clay-Organic Matter Complexes. In J. M. Bollag and G. Stotzky (Eds.). Soil Biochemistry, Vol. 6, Marcel Dekker, New York, pp. 1-28.
    • MIKESELL, M. D. and S. A. BOYD. 1990. Dechlorination of chloroform by Methanosarcina strains. Appl. Environ. Microbiol. 56:1198-1201.
    • BOYD, S. A. and L. E. SOMMERS. 1990. Humic and Fulvic Acid Fractions from Sewage Sludges and Sludge-Amended Soils. Humic Substances in Crop and Soil Sciences, Soil Science Society of America. Madison, Wisconsin, pp. 203-220.
    • CHIOU, C. T., J. F. LEE and S. A. BOYD. 1990. The surface area of soil organic matter. Environ. Sci. Technol., 24:1164-1166.
    • BOYD, S. A., J. XIANGCAN and J. F. LEE. 1990. Sorption of nonionic organic compounds by corn residues from a no-tillage field. J. Environ. Qual. 19:734-738.


    Progress 01/01/89 to 12/30/89

    Outputs
    Three major research initiatives are currently in progress: We have continued our studies on the sorptive interactions of organic contaminants with natural and modified soils and clays. The sorptive properties of clays and soils can be greatly enhanced by chemical modifications that we have developed. This technology, which is based on ion exchange reactions of organic cations for natural inorganic exchange ions, provide a simple, economical and effective approach for preventing the migration of organic contaminants into the subsurface and ground waters. The role of residual petroleum and PCB oils as sorptive phases in contaminated soil has also been established. Anaerobic reductive dechlorination reactions by bacteria found in sediments have been demonstrated for PCBs and other pollutants. In this reaction, bacteria remove chlorine directly from the organochlorine toxicant rendering the compound less toxic and less persistent. Pure cultures of methanogens have also been shown to dechlorinate chlorinated solvents such as TCE and PCE which are among the most common ground water contaminants. The influence of sorption/desorption reactions on the bioavailability (and thus biodegradability) of soil-bound contaminants is being studied. This is a new research area this year. Initial experiments on soils with a history of Simazine use indicated that the aged soil-bound pesticide residues are slow to desorb and are inaccessible to microbial degraders.

    Impacts
    (N/A)

    Publications

    • LEE, J.F., CRUM, J.M. and BOYD, S.A. 1989. Enhanced retention of organic contaminants by soils exchanged with organic cations. Environ. Sci. Technol. 23:1365-1372.
    • LEE, J.F., MORTLAND, M.M., CHIOU, C.T. and BOYD, S.A. 1989. Shape selective adsorption of aromatic molecules from water by tetramethylammonium-smectite. J. Chem. Soc. Faraday Trans. I. 85:2953-2962.
    • MORTLAND, M.M. and BOYD, S.A. 1989. Polymerization and dechlorination of chlororoethenes on Cu (II)-smectite via radical cation intermediates. Environ. Sci. Technol. 23:223-227.
    • BOYD, S.A., MIKESELL, M.D. and LEE, J.F. 1989. "Chlorophenols in Soils". In B.L. Sawhney (ed.) Reactions and Movement of Organic Chemicals in Soils, Soil Science Soc. of Amer. Special Publication No. 22, Madison, Wisconsin. pp 209=228.