Characterizing the Impact of Cyanobacterial Blooms on the Photoreactivity of Surface Waters from New York Lakes: A Combined Statewide Survey and Laboratory Investigation.

Cyanobacterial blooms introduce autochthonous dissolved organic matter (DOM) into aquatic environments, but their impact on surface water photoreactivity has not been investigated through collaborative field sampling with comparative laboratory assessments. In this work, we quantified the apparent quantum yields (Φapp,RI) of reactive intermediates (RIs), including excited triplet states of dissolved organic matter (3DOM*), singlet oxygen (1O2), and hydroxyl radicals (•OH), for whole water samples collected by citizen volunteers from more than 100 New York lakes. Multiple comparisons tests and orthogonal partial least-squares analysis identified the level of cyanobacterial chlorophyll a as a key factor in explaining the enhanced photoreactivity of whole water samples sourced from bloom-impacted lakes. Laboratory recultivation of bloom samples in bloom-free lake water demonstrated that apparent increases in Φapp,RI during cyanobacterial growth were likely driven by the production of photoreactive moieties through the heterotrophic transformation of freshly produced labile bloom exudates. Cyanobacterial proliferation also altered the energy distribution of 3DOM* and contributed to the accelerated transformation of protriptyline, a model organic micropollutant susceptible to photosensitized reactions, under simulated sunlight conditions. Overall, our study provides insights into the relationship between the photoreactivity of surface waters and the limnological characteristics and trophic state of lakes and highlights the relevance of cyanobacterial abundance in predicting the photoreactivity of bloom-impacted surface waters.

Coupling Suspect and Nontarget Screening with Mass Balance Modeling to Characterize Organic Micropollutants in the Onondaga Lake-Three Rivers System.

Characterizing the occurrence, sources, and fate of organic micropollutants (OMPs) in lake-river systems serves as an important foundation for constraining the potential impacts of OMPs on the ecosystem functions of these critical landscape features. In this work, we combined suspect and nontarget screening with mass balance modeling to investigate OMP contamination in the Onondaga Lake-Three Rivers system of New York. Suspect and nontarget screening enabled by liquid chromatography-high-resolution mass spectrometry led to the confirmation and quantification of 105 OMPs in water samples collected throughout the lake-river system, which were grouped by their concentration patterns into wastewater-derived and mixed-source clusters via hierarchical cluster analysis. Four of these OMPs (i.e., galaxolidone, diphenylphosphinic acid, N-butylbenzenesulfonamide, and triisopropanolamine) were prioritized and identified by nontarget screening based on their characteristic vertical distribution patterns during thermal stratification in Onondaga Lake. Mass balance modeling performed using the concentration and discharge data highlighted the export of OMPs from Onondaga Lake to the Three Rivers as a major contributor to the OMP budget in this lake-river system. Overall, this work demonstrated the utility of an integrated screening and modeling framework that can be adapted for OMP characterization, fate assessment, and load apportionment in similar surface water systems.

Organic Micropollutants in New York Lakes: A Statewide Citizen Science Occurrence Study.

The widespread occurrence of organic micropollutants (OMPs) is a challenge for aquatic ecosystem management, and closing the gaps in risk assessment of OMPs requires a data-driven approach. One promising tool for increasing the spatiotemporal coverage of OMP data sets is through the active involvement of citizen volunteers to expand the scale of OMP monitoring. Working collaboratively with volunteers from the Citizens Statewide Lake Assessment Program (CSLAP), we conducted the first statewide study on OMP occurrence in surface waters of New York lakes. Samples collected by CSLAP volunteers were analyzed for OMPs by a suspect screening method based on mixed-mode solid-phase extraction and liquid chromatography-high resolution mass spectrometry. Sixty-five OMPs were confirmed and quantified in samples from 111 lakes across New York. Hierarchical clustering of OMP occurrence data revealed the relevance of 11 most frequently detected OMPs for classifying the contamination status of lakes. Partial least squares regression and multiple linear regression analyses prioritized three water quality parameters linked to agricultural and developed land uses (i.e., total dissolved nitrogen, specific conductance, and a wastewater-derived fluorescent organic matter component) as the best combination of predictors that partly explained the interlake variability in OMP occurrence. Lastly, the exposure-activity ratio approach identified the potential for biological effects associated with detected OMPs that warrant further biomonitoring studies. Overall, this work demonstrated the feasibility of incorporating citizen science approaches into the regional impact assessment of OMPs.

Factors diminishing the effectiveness of phosphorus loading from municipal effluent: critical information for TMDL analyses.

Factors that diminish the effectiveness of phosphorus inputs from a municipal wastewater treatment facility (Metro) in contributing to phosphorus levels and its availability to support algae growth in a culturally eutrophic urban lake (Onondaga Lake, NY) were characterized and quantified. These factors included the bioavailability and settling characteristics of particulate phosphorus from this effluent, the dominant form (70%) of phosphorus in this input, and the plunging of the discharge to stratified layers in the lake. Supporting studies included: (1) chemical and morphometric characterization of the phosphorus-enriched particles of this effluent, compared to particle populations of the tributaries and lake, with an individual particle analysis technique; (2) conduct of algal bioavailability assays of the particulate phosphorus of the effluent; (3) conduct of multiple size class settling velocity measurements on effluent particles; and (4) determinations of the propensity of the discharge to plunge, and documentation of plunging through three-dimensional monitoring of a tracer adjoining the outfall. All of these diminishing effects were found to be operative for the Metro effluent in Onondaga Lake and will be integrated into a forthcoming phosphorus "total maximum daily load" analysis for the lake, through appropriate representation in a supporting mechanistic water quality model. The particulate phosphorus in the effluent was associated entirely with Fe-rich particles formed in the phosphorus treatment process. These particles did not contribute to concentrations in pelagic portions of the lake, due to local deposition associated with their large size. Moreover, this particulate phosphorus was found to be nearly entirely unavailable to support algae growth. While substantial differences are to be expected for various inputs, the effective loading concept and the approaches adopted here to assess the diminishing factors are broadly applicable.