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Linking Land, Air and Water Management in the Southern Everglades and Coastal Zone to Water Quality and Ecosystem Restoration: Task 2, Sulfur and Nutrient Contamination, Biogeochemical Cycling, and Effects

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Metadata:


Identification_Information:
Citation:
Citation_Information:
Originator:
William H. Orem

David P. Krabbenhoft; George R. Aiken

Publication_Date: 2001
Title:
Linking Land, Air and Water Management in the Southern Everglades and Coastal Zone to Water Quality and Ecosystem Restoration: Task 2, Sulfur and Nutrient Contamination, Biogeochemical Cycling, and Effects
Geospatial_Data_Presentation_Form: project
Online_Linkage:
<https://sofia.usgs.gov/projects/index.php?project_url=int_geochem_nutrients>
Description:
Abstract:
The scientific focus of this project is to examine the complex interactions (synergistic and antagonistic) of contaminants (externally derived nutrients, mercury, sulfur, pesticides, herbicides, polycyclic aromatic and aliphatic hydrocarbons, and other metals), ecosystem responses to variations in contaminant loading (time and space dimensions), and how imminent ecosystem restoration steps may affect existing contaminant pools.

The major objectives of this project are to use an integrated biogeochemical approach to examine: (1) anthropogenic-induced changes in the water chemistry of the Everglades ecosystem, (2) biogeochemical processes within the ecosystem affecting water chemistry, and (3) the predicted impacts of restoration efforts on water chemistry. The project uses a combination of field investigations, experimental approaches (mesocosm experiments in the ecosystem, and controlled laboratory experiments), and modeling to achieve these objectives. Contaminants of concern will include nutrients, sulfur, mercury, organic compounds, and other metals. Protocols for the collection of samples and chemical analyses developed during earlier studies will be employed in these efforts. Integration of the individual tasks within the project is achieved by colocation of field sampling sites, and cooperative planning and execution of laboratory and mesocosm experiments.

Data available for this project include dissolved sulfate and solid sulfur geochemistry and surface and pore water chemistry.

Purpose:
This project is an integration of a number of individual but interrelated tasks that address environmental impacts in the south Florida ecosystem using geochemical approaches. The Everglades restoration program is prescribing ecosystem-wide changes to some of the physical, hydrological, and chemical components of this ecosystem. However, it reamins uncertain what overall effects will occur as these components react to the perturbations especially of the biological and chemical components and toward what type of "new ecosystem" the Everglades will evolve. Results of these geochemical investigations will provide the critical elements for building ecosystem models and screening-level risk assessment for contaminants in the ecosystem.
Supplemental_Information:
This project is part of the combined Linking Land, Air and Water Managemenet in the Southern Everglades and Coastal Zone to Water Quality and Ecosystem Restoration project
Time_Period_of_Content:
Time_Period_Information:
Range_of_Dates/Times:
Beginning_Date: 20001001
Ending_Date: 20070930
Currentness_Reference: ground condition
Status:
Progress: In Work
Maintenance_and_Update_Frequency: As needed
Spatial_Domain:
Bounding_Coordinates:
West_Bounding_Coordinate: -82
East_Bounding_Coordinate: -80.1
North_Bounding_Coordinate: 28
South_Bounding_Coordinate: 24.4
Keywords:
Theme:
Theme_Keyword_Thesaurus: none
Theme_Keyword: hydrology
Theme_Keyword: chemistry
Theme_Keyword: geochemistry
Theme_Keyword: biogeochemistry
Theme_Keyword: nutrients
Theme_Keyword: sulfur
Theme_Keyword: contaminants
Theme_Keyword: Aquifer Storage and Recovery
Theme_Keyword: ASR
Theme_Keyword: organic matter
Theme:
Theme_Keyword_Thesaurus: ISO 19115 Topic Category
Theme_Keyword: environment
Theme_Keyword: inlandWaters
Theme_Keyword: 007
Theme_Keyword: 012
Theme_Keyword: geoscientificInformation
Theme_Keyword: 008
Place:
Place_Keyword_Thesaurus:
Department of Commerce, 1995, Countries, Dependencies, Areas of Special Sovereignty, and Their Principal Administrative Divisions, Federal Information Processing Standard (FIPS) 10-4, Washington, DC, National Institute of Standards and Technology
Place_Keyword: United States
Place_Keyword: US
Place:
Place_Keyword_Thesaurus:
U.S. Department of Commerce, 1987, Codes for the identification of the States, the District of Columbia and the outlying areas of the United States, and associated areas (Federal Information Processing Standard 5-2): Washington, DC, NIST
Place_Keyword: Florida
Place_Keyword: FL
Place:
Place_Keyword_Thesaurus:
Department of Commerce, 1990, Counties and Equivalent Entities of the United States, Its Possessions, and Associated Areas, FIPS 6-3, Washington, DC, National Institute of Standards and Technology
Place_Keyword: Broward County
Place_Keyword: Collier County
Place_Keyword: Glades County
Place_Keyword: Hendry county
Place_Keyword: Martin County
Place_Keyword: Miami-Dade County
Place_Keyword: Monroe County
Place_Keyword: Okeechobee County
Place:
Place_Keyword_Thesaurus: USGS Geographic Names Information System
Place_Keyword: Big Cypress National Preserve
Place_Keyword: Taylor Slough
Place_Keyword: Shark River Slough
Place_Keyword: Lake Ingraham East
Place_Keyword: Lake Okeechobee
Place_Keyword: Ten Thousand Islands
Place:
Place_Keyword_Thesaurus: none
Place_Keyword: Central Everglades
Place_Keyword: Florida Keys
Place_Keyword: SW Big Cypress
Place_Keyword: South East Coast
Place_Keyword: Greater Lake Okeechobee
Place_Keyword: EAA
Place_Keyword: Everglades Agricultural Area
Place_Keyword: Kissimmee River Basin
Place_Keyword: Kissimmee Valley
Place_Keyword: Water Conservation Area 1
Place_Keyword: Water Conservation Area 2A
Place_Keyword: Water Conservation Area 2B
Place_Keyword: Water Conservation Area 3A
Place_Keyword: WCA1
Place_Keyword: WCA2A
Place_Keyword: WCA2B
Place_Keyword: WCA3A
Access_Constraints: none
Use_Constraints:
none. Acknowledgement of the U.S. Geological Survey would be appreciated in products derived from or using these data.
Point_of_Contact:
Contact_Information:
Contact_Person_Primary:
Contact_Person: William Orem
Contact_Organization: U.S. Geological Survey
Contact_Address:
Address_Type: mailing address
Address: 956 National Center
City: Reston
State_or_Province: VA
Postal_Code: 20192
Country: USA
Contact_Voice_Telephone: 703 648-6273
Contact_Facsimile_Telephone: 703 648-6419
Contact_Electronic_Mail_Address: borem@usgs.gov
Browse_Graphic:
Browse_Graphic_File_Name:
<https://sofia.usgs.gov/publications/ofr/01-007/images/figure1b.gif>
Browse_Graphic_File_Description: Study areas in the northern Everglades of southern Florida
Browse_Graphic_File_Type: GIF
Data_Set_Credit:
Project personnel included Harry E. Lerch, Anne L. Bates, Robert A. Zielinski, Charles W. Holmes, Ben McPherson, Kathleen Simmons, Marci Marot, Margo Corum, and Marisa Beck.
Native_Data_Set_Environment: html tables
Cross_Reference:
Citation_Information:
Originator:
Haitzer, M.

Aiken, G. R.; Ryan, J. N.

Publication_Date: 2002
Title:
Binding of Mercury (II) to Dissolved Organic Matter: The Role of the Mercury-to-DOM Concentration Ration
Geospatial_Data_Presentation_Form: publication
Series_Information:
Series_Name: Environmental Science and Technology
Issue_Identification: v. 36, n. 16, p. 3564-3570
Publication_Information:
Publication_Place: Washington, DC
Publisher: American Chemical Society
Other_Citation_Details:
accessed as of 5/31/2011

The full article is available via journal subscription or single article purchase. The abstract, tables, figures, and bibliography are available at <https://sofia.usgs.gov/publications/papers/hg_dom_binding/>

Online_Linkage: <http://pubs.acs.org/doi/full/10.1021/es025699i>
Online_Linkage: <https://sofia.usgs.gov/publications/papers/hg_dom_binding/>
Cross_Reference:
Citation_Information:
Originator:
Bates, A. L.

Orem, W. H.; Harvey, J.. W.; Spiker, E. C.

Publication_Date: 2001
Title:
Geochemistry of Sulfur in the Florida Everglades: 1994 through 1999
Geospatial_Data_Presentation_Form: publication
Series_Information:
Series_Name: USGS Open-File Report
Issue_Identification: 01-007
Publication_Information:
Publication_Place: Tallahassee, FL
Publisher: U.S. Geological Survey
Other_Citation_Details: accessed as of 5/31/2011
Online_Linkage: <https://sofia.usgs.gov/publications/ofr/01-007/>
Cross_Reference:
Citation_Information:
Originator:
Bates, Anne L

Orem, William H.; Harvey. Judson W.; Spiker, Elliot C.

Publication_Date: 2002
Title: Tracing sources of sulfur in the Florida Everglades
Geospatial_Data_Presentation_Form: publication
Series_Information:
Series_Name: Journal of Environmental Quality
Issue_Identification: v. 31, n. 1, p. 287-299
Publication_Information:
Publication_Place: Madison, WI
Publisher: American Society of Agronomy
Other_Citation_Details: accessed as of 5/31/2011
Online_Linkage:
<https://sofia.usgs.gov/publications/papers/trace_sulfur/JEnvironQual.pdf>
Cross_Reference:
Citation_Information:
Originator:
Gough, L. P.

Kotra, R. K.; Holmes, C. W.; Orem, W. H.; Hageman, P. L.; Briggs, P. H.; Meier, A. L.; Brown, Z. A.

Publication_Date: 2000
Title:
Regional Geochemistry of Metals in Organic-Rich Sediments, Sawgrass, and Surface Water from Taylor Slough, Florida
Geospatial_Data_Presentation_Form: publication
Series_Information:
Series_Name: USGS Open-File Report
Issue_Identification: 00-327
Publication_Information:
Publication_Place: Reston, VA
Publisher: U.S. Geological Survey
Other_Citation_Details: accessed as of 5/31/2011
Online_Linkage: <https://sofia.usgs.gov/publications/ofr/00-327/>
Cross_Reference:
Citation_Information:
Originator:
Bates, Annie L.

Spiker, Elliott C.; Holmes, Charles W.

Publication_Date: 1998
Title:
Speciation and isotopic composition of sedimentary sulfur in the Everglades, Florida, USA
Geospatial_Data_Presentation_Form: publication
Series_Information:
Series_Name: Chemical Geology
Issue_Identification: v. 146, n. 3-4, p. 155-170
Publication_Information:
Publication_Place: Amsterdam, Netherlands
Publisher: Elsevier
Other_Citation_Details:
accessed as of 5/31/2011

The full article is available via journal subscription or single article purchase. The abstract may be viewed on the website below.

Online_Linkage:
<http://www.sciencedirect.com/science/article/pii/S0009254198000084>
Cross_Reference:
Citation_Information:
Originator:
Orem, W. H.

Holmes, C. W.; Kendall. C.; Lerch, H. E.; Bates, A. L.; Silva, S. R.; Boylan, A.; Corum, M.; Marot, M.; Hedgman, C.

Publication_Date: 1999
Title:
Geochemistry of Florida Bay sediments: I. nutrient history at five sites in eastern and central Florida Bay
Geospatial_Data_Presentation_Form: publication
Series_Information:
Series_Name: Journal of Coastal Research
Issue_Identification: v. 15, n. 4, p. 1055-1071
Publication_Information:
Publication_Place: Royal Palm Beach, FL
Publisher: Coastal Research and Education Foundation (CERF)
Other_Citation_Details:
accessed as of 5/31/2011

The full article is available via journal subscription or single article purchase. The abstract may be viewed on the website below.

The first page of the article may be viewed on the www.jstor.org website

Online_Linkage: <https://sofia.usgs.gov/publications/papers/geochem_flbaysed>
Online_Linkage: <http://www.jstor.org/pss/4299024>
Cross_Reference:
Citation_Information:
Originator:
Orem, W. H.

Lerch, H. E.; Rawlik, P.

Publication_Date: 1997
Title:
Geochemistry of surface and pore water at USGS coring sites in wetlands of South Florida, 1994 and 1995
Geospatial_Data_Presentation_Form: publication
Series_Information:
Series_Name: USGS Open-File Report
Issue_Identification: 97-454
Publication_Information:
Publication_Place: Reston, VA
Publisher: U.S. Geological Survey
Other_Citation_Details: accessed as of 5/31/2011
Online_Linkage: <https://sofia.usgs.gov/publications/ofr/97-454>
Cross_Reference:
Citation_Information:
Originator: Orem, W. H.
Publication_Date: 2004
Title:
Impacts of sulfate contamination on the Florida Everglades ecosystem
Geospatial_Data_Presentation_Form: publication
Series_Information:
Series_Name: USGS Fact Sheet
Issue_Identification: 109-03
Publication_Information:
Publication_Place: Reston, VA
Publisher: U.S. Geological Survey
Other_Citation_Details: accessed as of 5/31/2011
Online_Linkage: <http://pubs.usgs.gov/fs/fs109-03/fs109-03.html>
Cross_Reference:
Citation_Information:
Originator:
Louda, J. W.

Loitz, J. W.; Melisiotis, A.; Orem, W.H.

Publication_Date: 2004
Title:
Potential sources of hydrogel stabilization of Florida Bay lime mud sediments and implications for organic matter preservation
Geospatial_Data_Presentation_Form: publication
Series_Information:
Series_Name: Journal of Coastal Research
Issue_Identification: v. 20, n.2, p. 448-463
Publication_Information:
Publication_Place: Royal Palm Beach, FL
Publisher: Coastal Education and Research Foundation (CERF)
Other_Citation_Details:
accessed as of 5/31/2011

The full article is available via journal subscription or single article purchase. The abstract may be viewed on the website below.

Online_Linkage:
<http://www.jcronline.org/doi/abs/10.2112/1551-5036%282004%29020%5B0448%3APSOHSO%5D2.0.CO%3B2>
Cross_Reference:
Citation_Information:
Originator:
Zielinski, R. A.

Orem, W. H.; Simmons, K. R.; Bohlen, P. J.

Publication_Date: 2006
Title:
Fertilizer-derived uranium and sulfur in rangeland soil and runoff: a case study in central Florida
Geospatial_Data_Presentation_Form: publication
Series_Information:
Series_Name: Water, Air, & Soil Pollution
Issue_Identification: v. 176, n 1-4, p. 163-183
Publication_Information:
Publication_Place: Dordrecht, Netherlands
Publisher: Springer Netherlands
Other_Citation_Details:
accessed as of 5/31/2011

Posted with permission from Springer Science and Business Media. Journal of Water, Air, & Soil Pollution, Jan 2006. © Springer 2006.

Online_Linkage: <https://sofia.usgs.gov/publications/papers/uranium_and_sulfur/>

Data_Quality_Information:
Logical_Consistency_Report: not applicable
Completeness_Report: not available
Lineage:
Process_Step:
Process_Description:
Phase I work showed that excess nutrients and sulfur which enter the Everglades from canal discharge originating in the Everglades Agricultural Area (EAA) have altered biotic assemblages within parts of the ecosystem. The extent of sulfur contamination in the Everglades was first documented by this team. Unnaturally high levels of sulfate entering the Everglades have increased concentrations of toxic hydrogen sulfide, and are a key control regulating methylmercury (MeHg) production. Mercury (Hg) contamination of the Everglades is one of the most severe cases on record. Phase I work revealed that Hg and MeHg distributions in water, sediment and biota show complex seasonal and spatial trends and that ecosystem wide MeHg levels are controlled by in situ microbial processes (i.e sulfate reduction).
Process_Date: 2001
Process_Step:
Process_Description:
Phase II emphasizes experimental studies to amplify and expand on phase I field results. This includes the use of environmental chambers (mesocosms), and laboratory studies (microcosms) to examine the effects of changing environmental conditions (increased contaminant loading, changes in hydroperiod, drought/fire) on contaminant concentrations and methylmercury production. Phase II work also includes contaminant (nutrients, sulfur, and organics) source, loading, sequestration, and cycling studies in portions of the ecosystem not previously targeted, including Lake Okeechobee and the Kissimmee River Basin, Big Cypress National Preserve, and Shark River Slough and the southwest coast.

During FY02, mesocosm experiments were conducted at several sites in the Everglades to test the effects of sulfate addition (3 concentration levels), inorganic mercury (3 concentration levels), DOC (2 concentration levels), inorganic mercury plus sulfate (3 concentration levels), and inorganic mercury plus DOC. Following the additions, changes in chemical species (methylmercury and other mercury species, sulfur species, DOC, nutrients, anions, cations, Fe and Mn, redox, conductivity, pH) and microbial activity (sulfate reduction and mercury methylation rates) are determined in surface water, porewater, and sediments in the mesocosms over time (usually followed for several months following the start of the experiment).

In FY02, we conducted laboratory microcosm experiments to examine the effects of drying and rewetting of Evergladesí peats on methylmercury production, mercury geochemistry, sulfur geochemistry, and nutrients.

The experimental approach to drought/burn and rewet experiments involves: (1) collection of a series of small cores from two sites (WCA 3A-15, and STA-2), (2) drying of these cores for different times in a laboratory under controlled conditions, (3) rewetting of these cores with water collected at the two core collection sites, and (4) analysis of surface water, porewater, and sediments in the rewetted cores at intervals of time following rewetting. Analytes measured in the samples included methylmercury and other mercury species, sulfur species, nutrients, anions, cations, DOC, and sediment parameters (organic carbon, total N, total P, total S, S species). Biological parameters measured included methylmercury production and sulfate reduction rates. The initial experiment was begun in March 2002 and is scheduled to end in September 2002.

Process_Date: 2002
Process_Step:
Process_Description:
FY 2003 planned work includes:

1. Mesocosm Studies Mesocosms are left open to the outside environment until experiments are to be run. During experiments, mesocosms are closed off and chemical additions are made to sets of mesocosms to test the effects of the chemical additions on methylmercury production. Each chemical addition (variable) is tested at multiple concentration levels. In some sets of mesocosms, multiple chemical species are added to examine interactive effects.

We also propose to follow-up on our previous mesocosm studies on methylmercury production. Experiments will be repeated in order to verify and expand on results from FY02. A new feature in FY03 will be the use of isotopically labeled sulfate in the chemical additions to follow changes in sulfur geochemistry and its effects on methylmercury production. Our previous mesocosm experiments were focused in the northern Everglades. In FY03 we plan to add another mesocosm site in an STA (probably STA-2). These constructed wetlands can behave as zones of low methymercury production (such as ENR), but also can produce very high levels of methylmercury (STA-2). The reasons for this are not fully understood, and mesocosm experiments in the STAís will be designed to provide managers with information on how best to operate the STAís to minimize methylmercury production. Completed 2003

2. ) Drought/Burn and Rewet Experiments We will continue to analyze samples from the first drought/rewet experiment that ended in September 2002. Results from all experiment PIís will be combined in a database, and a series of publications on the results will be written up for publication. A follow-up experiment will be conducted in FY03 (continuing into FY04) using a larger core approach at two new sites (a high sulfur and low sulfur site in the northern Everglades). The larger cores will slow down the drying process in the lab, and more closely simulate conditions in the ecosystem. Additional changes to the follow-up experiment will include shorter dry times and extended sampling times following rewet. Results will provide ecosystem managers, and CERP/GEER planners with information on how to limit the effects of drought and rewet cycles on methylmercury production. Results will be especially useful for managing STAís and northern WCA 3, areas that experience more frequent drought/rewet cycles.

3. Nutrient and Sulfur Sources in Big Cypress Surface water, groundwater, porewater, and sediment cores will be collected from sites throughout the Big Cypress Preserve. Although much of Big Cypress is a sandy soil, there are areas where peat or peaty muck is present and shallow cores and porewater can be obtained. Groundwater will be obtained from existing wells in the Preserve. Samples will be analyzed for nutrients (carbon, nitrogen, and phosphorus), sulfur species, sulfur isotopic composition, uranium, and uranium activity ratio. The uranium and uranium activity ratio is used as a tracer for phosphorus sources. Orem, Zielinski, and Simmons have used this approach successfully to examine the sources of phosphorus to the northern Everglades, and to the rivers north of Lake Okeechobee. This approach can differentiate uranium (and phosphate) originating from agriculture, groundwater, and background. Similarly, sulfur isotopes will be used to trace the sources of sulfur entering Big Cypress. Orem/Bates/Lerch previously used sulfur isotopes to trace the sources of excess sulfate entering the northern Everglades.

In FY03 work will focus on sampling at selected sites throughout the Preserve, and chemical analysis of the samples. The study area will extend from the agricultural region north of the Big Cypress Preserve to the Ten Thousand Islands Area in the south. Sites will be primarily accessed by ground vehicle, but we will also explore possible helicopter support from the Big Cypress National Preserve for accessing more remote sites. Preliminary studies completed in 2003.

4.Aquifer Storage and Recovery (ASR) Water Quality Sampling of ASR experimental sites will be done in collaboration with the ASR science team, and with other members of this project looking at mercury (Krabbenhoft) and DOC (Aiken) water quality issues related to ASR. Sulfur species will be collected using a standard sampling protocol and analytical scheme, similar to that used in our work on sulfur contamination from canal discharge. In addition to sulfur species (sulfate, sulfide, thiosulfate, sulfite, total S), we will also examine the isotopic composition of the sulfur in the ASR water. This could then potentially be used to examine the fate of sulfur released from ASR water into the ecosystem. Sulfur isotope analysis delta 34S will involve isolation of the sulfate or sulfide using a precipitation approach, and measurement of the isotopic composition of the sulfur using isotope ratio mass spectrometry. We have used this approach previously to trace the sources of sulfur entering the Everglades.

Work on sulfur in ASR water in FY03 involves collaborative sampling with Krabbenhoft, Aiken, and others at selected ASR test sites. A series of preliminary samples will examine the range of sulfur concentration and speciation in ASR water, and the isotopic composition of this water.

5.Florida Bay Mercury Methylation and Sulfur Biogeochemistry The ACME II group (Krabbenhoft/Orem/Aiken) will examine the biogeochemistry of mercury methylation in Florida Bay sediments using a multifaceted field approach. This task will concentrate on evaluating the biogeochemistry of sulfur in Florida sediments and porewater. We will examine sulfur speciation and concentrations in sediments and sediment porewater. We have previously sampled in Florida Bay (1996-2001) and are familiar with the problems of coring and porewater extraction in the carbonate ooze underlying much of the bay. We will use an analytical scheme for sulfur speciation and quantification of sulfur species that we used previously in the Everglades and Florida Bay.

FY03 Work - Preliminary coring and porewater sampling to be conducted at selected sites nearshore and offshore in Florida Bay. Sampling to be conducted in collaboration with Krabbenhoft and Aiken.

Process_Date: 2003
Process_Step:
Process_Description:
Major efforts during FY04 included the following research studies:

(1) Sulfur Toxicity Experiment - A major effort in FY04 was the initiation of a sulfur toxicity experiment in WCA 3A. This experiment will test the hypothesis that excess sulfate entering the Everglades from agricultural runoff has a significant effect on macrophytes in the ecosystem. Sulfate entering the system diffuses into anoxic sediments and is reduced to sulfide. Sulfide toxicity has been shown in several environments to negatively impact freshwater aquatic plants. Current thinking is that excess phosphorus entering the ecosystem in agricultural runoff accounts for the change in macrophyte species (cattails displacing sawgrass) observed in WCA 2A. However, excess sulfate and subsequent buildup of sulfide in sediment porewater may also be a factor. A total of 30 mesocosms were placed in central WCA 3A in FY03; half in sawgrass and half in cattails. Dosing of these mesocosms with varying amounts of sulfate began in November 2003 and will continue through November 2006. Initial sampling of the mesocosms began in November, and follow up sampling was conducted in March and September 2004. Sampling includes geochemical studies of surface water, porewater, and sediments, and biological studies of macrophytes and microbial populations. Collaborators include D. Krabbenhoft (USGS), C. Gilmour (Smithsonian), I. Mendelssohn (LSU), and G. Aiken (USGS).

(2) Mercury Mesocosm Studies - This experiment begun in FY03 is testing the effect of additions of sulfate, Hg, and DOC on methylmercury (MeHg) production in the Everglades. Task 1 of the project examines the sulfur, major anion, and nutrient geochemistry of the mesocosms. In conjunction with mercury studies conducted by others (Krabbenhoft-USGS and Gilmour-Smithsonian) and DOC work (Aiken-USGS), the study provides fundamental information on the major processes controlling MeHg production in the Everglades. Mesocsoms were sampled in November 2003, March 2004, and September 2004. Results to date show that added sulfate stimulates MeHg production up to concentrations of about 15 mg/l, but depresses MeHg production above this concentration due to sulfide inhibition effects. This study is scheduled for completion in November 2004. A presentation on this work was completed in FY04.

(3) Big Cypress National Preserve (BCNP) - Analyses of samples from a preliminary water quality survey of BCNP were completed in FY04, including the first Hg and MeHg data for the Preserve. The soil MeHg levels at some sites are rather high (0.1 to 8 ng/g MeHg), but the reasons for this are presently unknown. Sulfate concentrations in surface water from within BCNP are low, but some canals external to BCNP (notably L28), have relatively high sulfate concentrations. A concern is that movement of sulfate-contaminated canal water from L28 or other canals into BCNP to enhance water levels may have the unwanted effect of stimulating MeHg production. A presentation and paper on this work will be completed in FY04.

(4) Other - (a) Collaboration with Paul McCormick (USGS) of sulfur geochemistry of WCA 1 (Loxahatchee NWR). (b) Completed yearly monitoring of canal sites in EAA and the Everglades for sulfate concentration and sulfur isotope composition; 32 samples analyzed and put into database

Process_Date: 2004
Process_Step:
Process_Description:
Major efforts during FY05 included the following research studies:

(1) Sulfur Toxicity Experiment - A major effort in FY05 was the continuation of a sulfur toxicity experiment in WCA 3A. This experiment tests the hypothesis that excess sulfate entering the Everglades from agricultural runoff has a significant effect on biogeochemistry, macrophyte growth, and the microbial community in the ecosystem. Sulfate entering the system diffuses into anoxic sediments and is reduced to sulfide. Sulfide toxicity has been shown in several environments to negatively impact freshwater aquatic plants. Current thinking is that excess phosphorus entering the ecosystem in agricultural runoff accounts for the change in macrophyte species (cattails displacing sawgrass) observed in WCA 2A. However, excess sulfate and subsequent buildup of sulfide in sediment porewater may also be a factor. A total of 30 mesocosms were placed in central WCA 3A in FY03; half in sawgrass and half in cattails. Dosing of these mesocosms with varying amounts of sulfate began in November 2003 and will continue through November 2006. Sampling of the mesocosms was conducted in November, 2004, and March and August 2005. Sampling includes geochemical studies of surface water, porewater, and sediments, and biological studies of macrophytes, microbial populations, and infauna.

(2) Mercury Methylation in Coastal Environments - Initial work is focused on a survey of coastal sites in Florida bay and the SW coast to examine the concentrations and biogeochemical processes influencing methylmercury production and bioaccumulation. In FY05, a total of 7 sites along the SW coast of Florida were sampled for surface water, pore water, and sediments. Samples were analyzed for mercury species, sulfur species, nutrients..

(3) Mercury Mesocosm Studies - This experiment begun in FY03 tested the effect of additions of sulfate, Hg, and methylmercury (MeHg) production in the Everglades. Task 1 of the project examines the sulfur, major anion, and nutrient geochemistry of the mesocosms. Mesocosms were sampled in November 2003, March 2004, and September 2004. This study was completed in FY05, and results presented at the Restoration Science Meeting held in Orlando in December 2004.

(4) Big Cypress National Preserve (BCNP)- Analyses of samples from a preliminary water quality survey (December 2003) of were completed in FY05, including the first Hg and MeHg data for the Preserve. A follow-up field survey during the wet season (August 2005) was also conducted. The soil MeHg levels at some sites are rather high (0.1 to 8 ng/g MeHg), but the reasons for this are presently unknown. Results of the first survey were presented at the Restoration Science Conference in Orlando in December 2004.

(5) Other - (a) Collaboration with Paul McCormick (USGS) of sulfur geochemistry of WCA 1 (Loxahatchee NWR). (b) Completed yearly monitoring of canal sites in EAA and the Everglades for sulfate concentration and sulfur isotope composition; 32 samples analyzed and put into database.

Process_Date: 2005
Process_Step:
Process_Description:
Work planned for 2006:

(1) Sulfur Toxicity Experiment - This experiment will continue in FY06, with major sampling efforts in November 2005, and March and August 2006. The experiment tests the hypothesis that excess sulfate entering the Everglades from agricultural runoff has a toxicological impact on native macrophytes in the ecosystem. Sulfate entering the system diffuses into anoxic sediments and is reduced to sulfide. Sulfide toxicity has been shown in several environments to negatively impact freshwater aquatic plants. The current experiment will test the hypothesis that excess sulfate entering the Everglades from agricultural runoff has a significant effect on macrophytes in the ecosystem. A total of 30 mesocosms were placed in central WCA 3A in FY03; half in sawgrass and half in cattails. Monthly dosing of these mesocosms with varying amounts of sulfate began in November 2003 and will continue through November 2006. Sampling includes geochemical studies of surface water, porewater, and sediments, and biological studies of macrophytes and microbial populations.

(2) Iron/Selenium Mesocosm Experiment - This experiment begun in FY05 is testing the effect of additions of iron and selenium on methylmercury (MeHg) production in the Everglades. Task 1 of the project examines the sulfur, major anion, and nutrient geochemistry of the mesocosms. In conjunction with mercury studies conducted by others (Krabbenhoft-USGS and Gilmour-Smithsonian) and USGS), the study provides fundamental information on the major processes controlling MeHg production in the Everglades. The initial experiment was begun with iron additions into mesocosms set up in WCA 3A in June 2005. Work is closely coordinated with Task 2 of this project (Krabbenhoft et al.). Work in FY06 will focus on analysis of samples collected in June and August 2005, and on additional sampling in FY06 (Fall, winter, and summer). This experiment provides information supporting the Comprehensive Integrated Water Quality Feasibility Study in the Landscape Science needs of the DOI Science Plan, by examining links between water quality and ecosystem structure and function, identifying degraded parts of the ecosystem and quantifying links to contaminants (nutrients, sulfur, organics, and mercury). Results are incorporated into conceptual, mathematical, and risk assessment models of the Everglades ecosystem.

(3) Big Cypress National Preserve (BCNP) - Results from a preliminary water quality survey in BCNP conducted in FY04 indicate that some areas of BCNP have higher than anticipated methylmercury (MeHg) concentrations. Additional sampling was conducted in wet season (August 2005). While most of the Preserve has very low levels of sulfate, much higher concentrations are found in canals outside the Preserve, especially the L28. Restoration plans call for diverting water from the L28 into BCNP to increase water levels. Work in FY06 will include analysis of the samples collected in August 2005, and preparation of a preliminary report on the FY04 and 05 sampling in BCNP. We have proposed conducting further field and mesocsom studies of MeHg production in response to increased sulfate loads in BCNP, similar to studies we have already conducted in the central Everglades. Results will provide managers with information on the effects of diverting water of high sulfate concentrations into BCNP, so that costs and benefits of this planned diversion can be assessed. effects of restoration on contaminant loads and impacts of contaminants.

(4) MeHg Production in the Coastal Zone - Results of research conducted by this project in the Everglades, including field surveys, mesocosm studies, and laboratory experiments have provided a working model for MeHg production and bioaccumulation in the freshwater Everglades and similar environments. This model, however, does not appear to apply to coastal marine systems. Work in FY05 included initial survey sampling at 7 sites in the SW coastal area of the greater Everglades (June 2005) to examine the mechanism by which MeHg is produced in the coastal zone of the greater Everglades. Work in FY06 will focus on analysis of the samples collected in June 2005, as well as additional survey work. This task will specifically focus on the role of sulfur species in MeHg production in coastal environments, and how the process differs from the freshwater environment. Initial work in FY05 will focus on field surveys, similar to our approach in the freshwater Everglades. This will be followed by experimental work in later years.

(5) Other - (a) Collaboration with Krabbenhoft and Gilmour in surveys to establish MeHg hotspots in Everglades National Park.

(b) Collaboration with Gilmour and Krabbenhoft on STA MeHg and sulfur surveys. This addresses risks to wildlife from soil-borne contaminants (sulfur, mercury, organics), through studies of the effects of dry/rewet cycles

(c) Collaboration with Krabbenhoft and Gilmour on follow-up dry/rewet studies of MeHg production. This addresses risks to wildlife from soil-borne contaminants (sulfur, mercury, organics), through studies of the effects of dry/rewet cycles

(d) We will continue collaboration with Paul McCormick on water quality in WCA 1 (Loxahatchee NWR), specifically focused on sulfur geochemistry and the paleoenvironmental chemical conditions in WCA 1. This supports the Arthur R. Marshall Loxahatchee NWR Internal Canal Structure Project by addressing the impacts of water quality (sulfur/nutrients/mercury) and water management practices on refuge resources.

(e) We will continue monitoring of canal sites for sulfate concentration and sulfur isotope composition.

Process_Date: 2006
Process_Step:
Process_Description:
Work planned for FY 2007 included:

To ensure comparability and interpretation of our results, the surveys will be conducted using the same sampling and analytical protocols developed under the ACME program. These include many mercury-free methods developed by the USGS and adopted world wide. The data string for water, sediment and gambusia presently available for site 3A15 (from March 1995 through December 2006) is one of the longest and most well documented data trend lines for mercury and methylmercury anywhere in the world. The fact that the data have been all derived from the same field crews and analytical lab adds considerable reliability and interpretability of the data, and have been the central data upon which many of our conclusions regarding the relative importance of the components of the "mercury axis of evil" (mercury, sulfate and carbon). We believe continuity of this data string is critical to infer how the restoration will affect the biogeochemistry of the Everglades. In addition, with the passage of national laws to reduce mercury emissions by 70%, trend lines like those at site 3A15 will be critical for providing direct evidence and quantifying the environmental benefits of such laws. Surveys conducted in portions of the Everglades not well covered by the ACME project will serve to provide an initial assessment of mercury/methylmercury contamination levels. Samples will be taken during early spring (February) and summer (July), when generally the annual low and high methylmercury levels are observed, respectively. All sampling efforts will include the collection of water, sediment, and gambusia, and will be analyzed using the low-level, mercury-speciation techniques applied by the USGS, Mercury Research Lab in Middleton, Wisconsin.

A limited number of coastal mangrove areas sampled in the summer of 2006 revealed some of the highest methylmercury levels ever seen by the USGS Mercury Research Lab (25 ng/L compared to Everglades typical interior marsh levels of about 0.05 to 0.50 ng/L). As of yet, no one has conducted a systematic study of the reasons underlying the very high levels of sport fish and commercial fish in Florida Bay, but the high levels observed in this initial survey would suggest the coastal, or near coastal zone, aquatic ecosystems could be a driving factor. For this part of our work plan, we will resample the locations sampled under the 2006 survey and add additional sites to our network to determine how generally applicable the initial observations are. During FY05 and FY06, we participated in a multi-agency sponsored effort to evaluate the possible toxicological significance of sulfate loading on indigenous plants of the Everglades. Although this experiment was specifically designed to examine sulfate cycling and toxicity, it presented a good opportunity to extend our observations to assess the sulfur-dose methylmercury-production response curve. In December 2006, a final sampling effort was conducted, and in which we sampled all 32 mesocosms plus two additional ambient control sites. Samples for sediment, water and gambusia were collected, and presently in the sample queue at the USGS Mercury Research Lab.

The mesocosm experiments conducted under ACME Phase II were very useful for testing our overall hypotheses related to the controlling influence of sulfate, carbon and mercury in the methylmercury generation process. These experiments also provided quantitative estimates of the relative importance of each of these controlling components - the first time this has been done anywhere. However, we do not know how different our results may have been if the underlying substrate (peat in all our previous experiments) vary. For example, the marl prairies of ENP are largely refractory carbon and not as useable by microbial communities such as sulfate reducing bacteria. As such, ENP settings may have a greater response to added carbon that what we observed in the peat marshes of WCA 2 and WCA 3. The same could be true for the sandy substrate regions of BCNP. As part of the "Contaminant Synthesis" project, we will be compiling and publishing results from the previous mesocosm experiments. During this compilation and interpretation process, we will identify any critical needs or unanswered questions that those experiments generated. In addition, results from the surveys conducted in the FY07 will be available and used in combination with the previous mesocosm experiments to design a final round of mesocosm experiment that will likely be conducted ENP, BCNP or LNWR.

Process_Date: 2007
Process_Step:
Process_Description:
Work planned for FY 2008:

We have proposed to extend our findings to relatively less well studied portions of the Everglades, especially those that may receive greater amounts of canal water discharge as a result of the restoration efforts (e.g., ENP, BCNP, and LNWR). This three year project will seek to extend our knowledge of the controlling factors of mercury toxicity in the Everglades, with specific attention to geographical areas and land use and changes related to the restoration that may affect methylmercury production and bioaccumulation. Because work under ACME was largely conducted in the WCA's, we propose to direct our current and future efforts on the federally managed lands. Three specific areas of work will be conducted in FY07: (1) sampling surveys on the federally managed lands, particularly those that are receiving canal water discharge; (2) sampling in the newly operating periphyton/limerock STAs and previously existing cattail/peat STAs; (3) sampling of the McCormick canal water dosing mesocosms in LNWR; (4) participation on the planning and execution of the Water Quality of the Greater Everglades: Fate and Transport of Nutrients and Other Contaminants symposium at the Spring 2008 GEER conference; and, (5) continued efforts toward publication of past and current results.

Process_Date: Not complete
Process_Contact:
Contact_Information:
Contact_Person_Primary:
Contact_Person: William H. Orem
Contact_Organization: U.S. Geological Survey
Contact_Position: Project Chief
Contact_Address:
Address_Type: mailing address
Address: 956 National Center
City: Reston
State_or_Province: VA
Postal_Code: 20192
Contact_Voice_Telephone: 703 648 6273
Contact_Facsimile_Telephone: 703 648 6419
Contact_Electronic_Mail_Address: borem@usgs.gov
Hours_of_Service: 9:00-6:00 M-F

Spatial_Data_Organization_Information:
Indirect_Spatial_Reference: southern Everglades and coastal zone

Spatial_Reference_Information:
Horizontal_Coordinate_System_Definition:
Geographic:
Latitude_Resolution: 0.001
Longitude_Resolution: 0.001
Geographic_Coordinate_Units: Degrees and decimal minutes
Geodetic_Model:
Horizontal_Datum_Name: North American Datum of 1983
Ellipsoid_Name: Geodetic Reference System 80
Semi-major_Axis: 6378137
Denominator_of_Flattening_Ratio: 298.257

Entity_and_Attribute_Information:
Overview_Description:
Entity_and_Attribute_Overview:
Data collected for solid phase sulfur geochemistry include: core segment, av. Depth in cm, sulfate % wet wt, AVS % wet wt, DS % wet wt, OS % wet wt, TS % wet wt, Sulfate 34S/32S. AVS 34S/32S, DS 34S/32S, and OS 34S/32S arranged by sampling location

Data collected for dissolved sulfate concentrations and isotopic compositions include: month and year of collection, sampling location, SO4 mg/l, SO4 meq/l, and SO4 34S/32S

Data collected for surface water and pore water include: core number, depth, pH, titration alkalinity, dissolved organic carbon, sulfide, sulfate, phosphate, ammonium, nitrate, chloride, fluoride, and bromide. Concentrations of major cations in pore water include data for sodium, potassium, calcium, magnesium, iron, strontium and silicon. Surface water values are indicated by a "0" in the depth column.

Entity_and_Attribute_Detail_Citation: USGS personel

Distribution_Information:
Distributor:
Contact_Information:
Contact_Person_Primary:
Contact_Person: Heather S. Henkel
Contact_Organization: U.S. Geological Survey
Contact_Address:
Address_Type: mailing address
Address: 600 Fourth St. South
City: St. Petersburg
State_or_Province: FL
Postal_Code: 33701
Country: USA
Contact_Voice_Telephone: 727 803-8747 ext 3028
Contact_Facsimile_Telephone: 727 803-2030
Contact_Electronic_Mail_Address: hhenkel@usgs.gov
Resource_Description: solid phase sulfur data
Distribution_Liability: No warrantees are implied or explicit for the data
Standard_Order_Process:
Digital_Form:
Digital_Transfer_Information:
Format_Name: tables
Digital_Transfer_Option:
Online_Option:
Computer_Contact_Information:
Network_Address:
Network_Resource_Name: <https://sofia.usgs.gov/publications/ofr/01-007/table1.html>
Network_Resource_Name: <https://sofia.usgs.gov/publications/ofr/01-007/table2.html>
Network_Resource_Name: <https://sofia.usgs.gov/publications/ofr/01-007/table3.html>
Network_Resource_Name: <https://sofia.usgs.gov/publications/ofr/01-007/table4.html>
Network_Resource_Name: <https://sofia.usgs.gov/publications/ofr/01-007/table5.html>
Access_Instructions: Data available from the SOFIA web site
Fees: none

Distribution_Information:
Distributor:
Contact_Information:
Contact_Person_Primary:
Contact_Person: Heather S. Henkel
Contact_Organization: U.S. Geological Survey
Contact_Address:
Address_Type: mailing address
Address: 600 Fourth St. South
City: St. Petersburg
State_or_Province: FL
Postal_Code: 33701
Country: USA
Contact_Voice_Telephone: 727 803-8747 ext 3028
Contact_Facsimile_Telephone: 727 803-2030
Contact_Electronic_Mail_Address: hhenkel@usgs.gov
Resource_Description: dissolved sulfate data
Distribution_Liability: No warrantees are implied or explicit for the data
Standard_Order_Process:
Digital_Form:
Digital_Transfer_Information:
Format_Name: tables
Digital_Transfer_Option:
Online_Option:
Computer_Contact_Information:
Network_Address:
Network_Resource_Name: <https://sofia.usgs.gov/publications/ofr/01-007/table6.html>
Network_Resource_Name: <https://sofia.usgs.gov/publications/ofr/01-007/table7.html>
Network_Resource_Name: <https://sofia.usgs.gov/publications/ofr/01-007/table8.html>
Access_Instructions: Data available from the SOFIA web site
Fees: none

Distribution_Information:
Distributor:
Contact_Information:
Contact_Person_Primary:
Contact_Person: Heather S. Henkel
Contact_Organization: U.S. Geological Survey
Contact_Address:
Address_Type: mailing address
Address: 600 Fourth St. South
City: St. Petersburg
State_or_Province: FL
Postal_Code: 33701
Country: USA
Contact_Voice_Telephone: 727 803-8747 ext 3028
Contact_Facsimile_Telephone: 727 803-2030
Contact_Electronic_Mail_Address: hhenkel@usgs.gov
Resource_Description: surface/pore water chemistry data
Distribution_Liability: No warrantees are implied or explicit for the data
Standard_Order_Process:
Digital_Form:
Digital_Transfer_Information:
Format_Name: tables
Digital_Transfer_Option:
Online_Option:
Computer_Contact_Information:
Network_Address:
Network_Resource_Name: <https://sofia.usgs.gov/publications/ofr/97-454/table3.html>
Network_Resource_Name: <https://sofia.usgs.gov/publications/ofr/97-454/table4.html>
Access_Instructions: Data available from the SOFIA web site
Fees: none

Metadata_Reference_Information:
Metadata_Date: 20110531
Metadata_Contact:
Contact_Information:
Contact_Person_Primary:
Contact_Person: Heather Henkel
Contact_Organization: U.S. Geological Survey
Contact_Address:
Address_Type: mailing and physical address
Address: 600 Fourth Street South
City: St. Petersburg
State_or_Province: FL
Postal_Code: 33701
Country: USA
Contact_Voice_Telephone: 727 803-8747 ext 3028
Contact_Facsimile_Telephone: 727 803-2030
Contact_Electronic_Mail_Address: sofia-metadata@usgs.gov
Metadata_Standard_Name: Content Standard for Digital Geospatial Metadata
Metadata_Standard_Version: FGDC-STD-001-1998
Metadata_Access_Constraints: none
Metadata_Use_Constraints:
This metadata record may have been copied from the SOFIA website and may not be the most recent version. Please check <https://sofia.usgs.gov/metadata> to be sure you have the most recent version

This page is <https://sofia.usgs.gov/metadata/sflwww/int_geochem_nutrients.html>

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