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2008 Progress Report: Monitoring, Photochemical Fate, and Oxidative Degradation by UV and Solar-based Catalytic Technologies of Cyanotoxins in Freshwater Estuaries

EPA Grant Number: R833223
Title: 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:

Task 1. Monitoring of Harmful Algal Blooms (HAB) and Sampling in the Great Lakes.
 
 Activities and Findings: Five utilities were selected for the 2008 Great Lakes Monitoring Study. Two utilities on Lake Michigan, one utility on Lake Erie, one utility on Lake Huron, and one on Lake St. Clair. These utilities were selected based on plant cyanobacteria data, taste and odor events, and occurrence of cyanobacteria blooms.  Table 1 describes the drinking water utilities.
 
Table 1: Drinking Water Utilities 2008 Study
 
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
 
 
Results: The utilities were very responsible at grabbing and mailing their samples to LSSU.  Huron I utility removed themselves from the study a week before the sampling was to begin.  Although all Great Lake sampling periods were mid summer to early fall, the start and finishing dates were utility specific (Table 2). Temperature, pH and turbidity were water quality parameters that were reported by the utility (Table 3). Of the 43 samples collected from the Great Lakes, 5 tested positive for microcystin (Table 4). Three variants of microcystin were reported, MCY LR, RR and YR. Microcystin LR was reported in Lake Michigan, Lake Erie, and Lake Huron, whereas MCY RR and YR were reported in Lake Huron. None of the Great Lake samples were above 1 ppb microcystin. Cylindrospermopsis was found in both Lakes Michigan and Erie. Although Microcystis was in each of the study lakes, its concentration was very low in all waters except Huron. Other toxin producing genera included Anabaenopsis, Anabaena, Oscillitoria, and Aphanizomenon. 
Three Midwestern lakes were included in this study; Muskegon Lake, MI, Mona Lake, MI and Budd Lake, MN. High levels of microcystin have been reported on each of these lakes. These lakes were added to the study to increase the likelihood of sampling a toxic cyanobacteria bloom. The only samples above 1 ppb microcystin were collected from Mona and Muskegon Lakes. Microcystin LR and YR were quantified from these southwestern Michigan lakes.   
 
Table 2: Summary of the 2008 Study Logistics
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
 
Table 3: Water Quality Summary
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
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

Publications Views
Other project views: All 54 publications 17 publications in selected types All 16 journal articles
Publications
Type Citation Project Document Sources
Journal Article 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)
  • Abstract from PubMed
  • Full-text: Environmental Science & Technology
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    • Journal Article 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)
  • Abstract from PubMed
  • Full-text: Science Direct
    Exit
  • Abstract: Science Direct
    Exit
  • Other: Science Direct
    Exit
    • Journal Article 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)
  • Full-text: Science Direct
    Exit
  • Abstract: Science Direct
    Exit
  • Other: Science Direct PDF
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    • Journal Article 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)
  • Abstract from PubMed

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