Grantee Research Project Results
2008 Progress Report: Monitoring, Photochemical Fate, and Oxidative Degradation by UV and Solar-based Catalytic Technologies of Cyanotoxins in Freshwater Estuaries
EPA Grant Number: R833223Title: Monitoring, Photochemical Fate, and Oxidative Degradation by UV and Solar-based Catalytic Technologies of Cyanotoxins in Freshwater Estuaries
Investigators: Dionysiou, Dionysios D. , Miller, Cheryl L. , Deis, Donald R. , Westrick, Judy , O'Shea, Kevin
Institution: University of Cincinnati , PBS&J , Florida International University , Lake Superior State University
Current Institution: University of Cincinnati , Florida International University , Green Water Laboratories/CyanoLab , Lake Superior State University , PBS&J
EPA Project Officer: Aja, Hayley
Project Period: April 1, 2007 through March 31, 2010
Project Period Covered by this Report: April 1, 2008 through March 31,2009
Project Amount: $679,589
RFA: Development and Evaluation of Innovative Approaches for the Quantitative Assessment of Pathogens in Drinking Water (2005) RFA Text | Recipients Lists
Research Category: Drinking Water , Water
Objective:
The specific objectives of the proposal are to: (1) evaluate the photolytic degradation of microcystins along a salinity and dissolved organic carbon (DOC) gradient and identify the fate and partitioning of microcystins in the estuarine portion of the lower St. Johns River in Florida and several locations in the Great Lakes; (2) investigate the mechanisms of the photo-transformations of cyanotoxins present in synthetic solutions and samples from the Great Lakes and Florida by visible and solar irradiation; (3) explore solar-driven catalytic systems for the destruction of cyanotoxins in water; and (4) investigate the fate of cyanotoxins under germicidal action UV (254 nm) (low pressure lamps) or broader spectrum (medium pressure lamps) at various levels of UV fluence in consideration with the presence of UV disinfection systems in several drinking water treatment plants.Progress Summary:
Lake
|
Location
|
Treatment
|
Intake Depth
|
Algae Data
|
Michigan I
Lake Bluff, IL
|
3,000 ft off shore
|
KMnO4 intake, conventional treatment with ozone, UV and chlorine
|
25 ft
|
Yes
|
Michigan II
Wyoming
|
4,440 ft off shore
|
Conventional
|
40-50 ft
|
Yes - not received yet
|
Erie I
Cleveland, Baldwin Plant
|
41.54844219, -81.7504091
|
Conventional treatment, free chlorine for primary and secondary disinfection, pre-oxidation with potassium permanganate, and powdered activated carbon for taste and odor control
|
10-25 ft
|
Yes - will send later
|
Huron I
Saginaw Bay
|
2 miles off shore
|
Source feeds in two storage reservoir, conventional treatment
|
45 ft
|
Yes
|
Huron II
Bay City
|
Latitude: 43.71N, Longitude: 83.90 W
|
Ozone, lime softening, conventional treatment
|
17 ft
|
Yes
|
Lake St. Clair
IRA
|
1,650 ft from the nearest road
|
Package plant with up flow clarifier filter mix media
|
6 ft
|
None
|
Lake
|
Start Date
|
Stop Date
|
Samples Taken
|
Samples Analyzed
|
Michigan I
|
7/9/08
|
9/02/08
|
6
|
6
|
Michigan II
|
7/9/08
|
8/27/08
|
7
|
7
|
Erie I
|
6/25/08
|
9/10/08
|
12
|
12
|
Huron I
|
Withdrew from the study before sampling started
|
|||
Huron II
|
6/24/08
|
9/15/08
|
13
|
12
|
Lake St. Clair
|
7/22/08
|
9/12/08
|
6
|
6
|
Muskegon Lake
|
7/22/08
|
8/02/08
|
3
|
3
|
Mona Lake
|
7/22/08
|
7/22/08
|
1
|
1
|
Budd Lake
|
|
|
2
|
2
|
Lake
|
Temperature
|
pH
|
Turbidity
|
# of positive source samples
|
Dominant cyanobacteria
|
Michigan I
|
13-22oC
|
7.8-8.4
|
0.7-2.2 NTU
|
0
|
None,<100 cells/mL
|
Michigan II
|
9-20oC
|
7.4-8.6
|
0.4-1.6 NTU
|
1
|
None, <100 cells/mL
|
Erie I
|
21-26oC
|
7.5-8.4
|
0.5-1.4 NTU
|
2
|
None, <100 cells/mL
|
Huron I
|
Withdrew from the study before sampling started
|
||||
Huron II
|
20-25oC
|
7.8-8.6
|
4.2-14.5 NTU
|
2
|
Microcystis, 9,500-1000 cells/mL
|
Lake St. Clair
|
20-24oC
|
7.4-8.8
|
1.5-3.1 NTU
|
0
|
None, 105 cells/mL
|
Muskegon Lake
|
26-27oC
|
8.8-9.2
|
70.2, 69.1- 266, 269
|
3
|
N/A
|
Mona Lake
|
N/A
|
N/A
|
N/A
|
1
|
N/A
|
Budd Lake
|
N/A
|
N/A
|
N/A
|
2
|
Aphanizomenon, 50,149 cells/mL
|
Sample Name
|
Date Taken
|
Algal Toxin Concentration (ug/L)
|
Sent to UoC
|
|
||
|
|
MCY-LR
|
MCY-YR
|
MCY-RR
|
|
|
Lake Erie
|
7/16/2008
|
0.56
|
|
|
XX
|
|
Lake Erie
|
7/23/2008
|
0.59
|
|
|
|
|
Lake Michigan II
|
7/23/2008
|
0.51
|
|
|
|
|
Huron II
|
7/28/2008
|
0.54
|
0.47
|
|
XX
|
|
Huron II
|
8/11/2008
|
0.33
|
|
0.27
|
|
|
Muskegon Lake Mix 001
|
7/22/2008
|
59
|
13
|
|
XX
|
|
Mona Lake Ross Park 001
|
7/22/2008
|
11
|
10
|
|
XX
|
Future Activities:
Task 1. Monitoring of HAB and Sampling in the Great Lakes
Five utilities were selected for the 2009 Great Lakes Monitoring Study. These utilities are located on Lakes Michigan, Huron and Erie. The Michigan III utility is on the west shores of Lake Michigan. The three utilities were selected from the west end of Lake Erie. The west end of the Lake Erie is noted for toxic cyanobacteria blooms. The three utilities include 2 small island communities and a medium size city. The 2 small island utility monitoring will be done in collaboration with Dr. Juli Dyble Bressie, NOAA. Dr. Julia Dyble Bressie has also agreed to sample for our study from the NOAA boats which will be located in Saginaw Bay, Lake Huron, and the west end of Lake Erie. In order to increase our likelihood of sampling a toxic cyanobacteria bloom, Dr. David Szlag, LSSU, will attempt to correlate harmful algal blooms with Moderate Resolution Imaging Spectroradiometer (MODIS) satellite data. The current Chlorophyll-a data product derived from MODIS 1 km resolution bands is fairly accurate for the open ocean environment but experience in the Baltic Sea suggests that it may not accurately reflect conditions in shallow or near shore environments. The MODIS chlorophyll-a product and water temperature will be correlated with cyanotoxin measurements in the lower Great Lakes. The MODIS satellites deliver images several times a day at one kilometer resolution.
Plant
|
Location
|
Treatment
|
Depth
|
Algae Data
|
Michigan III
|
44* 4' 31" N 87* 37' 17" W
|
Microfiltration Membranes, 500 micron pre-strainer, 0.2 micron membranes
|
28 ft
|
No
|
Erie II
|
2 miles NE of Cooley Canal entrance 41* 41' 58" N 83* 15' 58" W
|
Potassium permanganate, GAC, alum, lime, soda ash, Cl2, F-, alum coagulation, lime-soda ash softening plant
|
8-18 ft
|
No
|
Huron 2
|
Latitude: 43.71N, Longitude: 83.90 W
|
Ozone, lime softening, conventional treatment
|
17 ft
|
Yes
|
Erie III
|
|
|
|
|
Erie IV
|
|
|
|
|
Task 2. Monitoring of HAB and Photochemical Effects in St. Johns River in Florida
Similar to 2008, monthly water sampling in the St. Johns River between Crescent Lake and north of Doctors Lake (in the area of Plummers Cove) will be performed and analyzed for total and dissolved microcystin content. This extension in the geographical coverage within the SJR is intended to increase the salinity range of sample collection. Again, if a bloom event does occur in the St. Johns River 2L of dense algal material will be sent via overnight mail to the USEPA/University of Cincinnati and Florida International University on a as needed basis. Macro-invertebrate collection will be performed, if and when, microcystin concentrations are expected to be high (> 10 ug/L). Invertebrate sample collection will be performed on a as needed basis and will be dependent on bloom formation or toxin concentrations over time. Doctors Lake appears to be the best location for sample collection of bivalves. Microcystin analysis on tissues will be limited to unbound microcystins as a confirmed protocol for tissues currently does not exist at GreenWater Laboratories/CyanoLab. GreenWater Laboratories/CyanoLab is currently developing a protocol for the quantification of MMPB (a breakdown product of bound microcystin) in animal sera and once this protocol is successful an attempt will be made to perform similar analyses on tissues of bivalve
Task 3. Fundamental Studies in the Photochemical Fate and Transformation of Cyanotoxins
For the subsequent funding period, we are planning advanced and 2 dimensional NMR experiments in an attempt to characterize the products of DA degradation as a mixture, but given the liable nature of peroxide products, low temperature studies may be required for proper isolation. While TiO2 photocatalysis effectively destroy and detoxify PbTxs, practical application will require further catalyst development and careful economic analyses. Development of solar activated catalyst on floating substrates may offer an attractive solution for the degradation of PbTxs in marine estuaries. The accomplishments, expenditures, and outputs are consistent with the proposed timetable relative to the date the funding was awarded.
Task 4. Exploring Nitrogen-Containing Surfactants for the Synthesis of TiO2-xNx
For the subsequent period report, we will continue our investigations on the effect of various water matrix parameters (i.e., NOM, hardness, turbidity, alkalinity) on the photocatalytic degradation of MC-LR and other cyanotoxins using UV/H2O2 and modified TiO2 photocatalytic nanoparticles and films, under UV, visible and solar irradiation employing real and simulated sunlight. Mechanistic studies will be carried out to determine the intermediates under these conditions. We will also explore other methods to synthesized visible light activated TiO2 nanomaterials with high photocatalytic activity towards MC-LR and other cyanotoxins. The role of film porosity on the transport and interactions of cyanotoxins on the TiO2 surface will also be explored. Real water with cyanotoxins will be also be evaluated. The equipment, techniques and materials will be the same or similar as described in the publications in appendix B-D.
Journal Articles on this Report : 4 Displayed | Download in RIS Format
Other project views: | All 54 publications | 17 publications in selected types | All 16 journal articles |
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Type | Citation | ||
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Antoniou MG, Shoemaker JA, de la Cruz AA, Dionysiou DD. Unveiling new degradation intermediates/pathways from the photocatalytic degradation of microcystin-LR. Environmental Science & Technology 2008;42(23):8877-8883. |
R833223 (2008) R833223 (Final) |
Exit |
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Antoniou MG, Shoemaker JA, de la Cruz AA, Dionysiou DD. LC/MS/MS structure elucidation of reaction intermediates formed during the TiO2 photocatalysis of microcystin-LR. Toxicon 2008;51(6):1103-1118. |
R833223 (2008) R833223 (Final) |
Exit Exit Exit |
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Pelaez M, de la Cruz AA, Stathatos E, Falaras P, Dionysiou DD. Visible light-activated N-F-codoped TiO2 nanoparticles for the photocatalytic degradation of microcystin-LR in water. Catalysis Today 2009;144(1-2):19-25. |
R833223 (2008) R833223 (Final) |
Exit Exit Exit |
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Song W, Xu T, Cooper WJ, Dionysiou DD, de la Cruz AA, O’Shea KE. Radiolysis studies on the destruction of microcystin-LR in aqueous solution by hydroxyl radicals. Environmental Science & Technology 2009;43(5):1487-1492. |
R833223 (2008) R833223 (Final) |
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Progress and Final Reports:
Original AbstractThe perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Conclusions drawn by the principal investigators have not been reviewed by the Agency.