Automated Subdaily Sampling of Cyanobacterial Toxins on a Buoy Reveals New Temporal Patterns in Toxin Dynamics.

Temporal variability of toxins produced by cyanobacteria in lakes is relatively unknown at time scales relevant to public health (i.e., hourly). In this study, a water quality monitoring buoy was outfitted with an automated water sampler taking preserved samples every 6 h for 68.75 days over a drinking water intake. A total of 251 samples were analyzed by tandem mass spectrometry for 21 cyanotoxin congeners in 5 classes producing 5020 data points. Microcystins (MCs) were the most abundant toxins measured (mean ± sd = 3.9 ± 3.3 µg/L) followed by cyanopeptolins (CPs) (1.1 ± 1.5 µg/L), anabaenopeptins (APs) (1.0 ± 0.6 µg/L), anatoxin-a (AT-A) (0.03 ± 0.06 µg/L), and microginin-690 (MG-690) (0.002 ± 0.01 µg/L). Advanced time series analyses uncovered patterns in cyanotoxin production. The velocity of cyanotoxin concentration varied from -0.7 to 0.9 µg/L/h with a maximum positive velocity just prior to peak toxin concentration during nonbloom periods. A backward-looking moving window of variance analysis detected major increases in cyanotoxin concentration and predicted the two greatest increases in MC. A wavelet analysis identified a significant ( p < 0.01) 2.8-4.2 day periodicity in toxin concentration over a ∼25 day period during peak toxin production, which is partially explained by easterly wind velocity ( R = -0.2, p < 0.05). Diversity in congener profiles was explored with principle component analysis showing that cyanotoxin dynamics followed a seasonal trajectory where toxin profiles were significantly clustered (ANOSIM R = 0.7, p < 0.05) on a daily basis. Variability in toxin profiles was strongly correlated with time ( R = -0.8, p < 0.001) as well as the C:N ratio of the toxin pool ( R = 0.17, p < 0.05). The methods employed here should be useful for uncovering patterns in cyanotoxin dynamics in other systems.

Cyanobacterial Toxins of the Laurentian Great Lakes, Their Toxicological Effects, and Numerical Limits in Drinking Water.

Cyanobacteria are ubiquitous phototrophic bacteria that inhabit diverse environments across the planet. Seasonally, they dominate many eutrophic lakes impacted by excess nitrogen (N) and phosphorus (P) forming dense accumulations of biomass known as cyanobacterial harmful algal blooms or cyanoHABs. Their dominance in eutrophic lakes is attributed to a variety of unique adaptations including N and P concentrating mechanisms, N2 fixation, colony formation that inhibits predation, vertical movement via gas vesicles, and the production of toxic or otherwise bioactive molecules. While some of these molecules have been explored for their medicinal benefits, others are potent toxins harmful to humans, animals, and other wildlife known as cyanotoxins. In humans these cyanotoxins affect various tissues, including the liver, central and peripheral nervous system, kidneys, and reproductive organs among others. They induce acute effects at low doses in the parts-per-billion range and some are tumor promoters linked to chronic diseases such as liver and colorectal cancer. The occurrence of cyanoHABs and cyanotoxins in lakes presents challenges for maintaining safe recreational aquatic environments and the production of potable drinking water. CyanoHABs are a growing problem in the North American (Laurentian) Great Lakes basin. This review summarizes information on the occurrence of cyanoHABs in the Great Lakes, toxicological effects of cyanotoxins, and appropriate numerical limits on cyanotoxins in finished drinking water.

Analysis of cyanobacterial metabolites in surface and raw drinking waters reveals more than microcystin.

Freshwater cyanobacterial blooms are becoming increasingly problematic in regions that rely on surface waters for drinking water production. Microcystins (MCs) are toxic peptides produced by multiple cyanobacterial genera with a global occurrence. Cyanobacteria also produce a variety of other toxic and/or otherwise bioactive peptides (TBPs) that have gained less attention including cyanopeptolins (Cpts), anabaenopeptins (Apts), and microginins (Mgn). In this study, we compared temporal and spatial trends of four MCs (MCLR, MCRR, MCYR, MCLA), three Cpts (Cpt1020, Cpt1041, Cpt1007), two Apts (AptF, AptB), and Mgn690 in raw drinking water and at six surface water locations above these drinking water intakes in a eutrophic lake. All four MC congeners and five of six TBPs were detected in lake and raw drinking water. Across all samples, MCLR was the most frequently detected metabolite (100% of samples) followed by MCRR (97%) > Cpt1007 (74%) > MCYR (69%) > AptF (67%) > MCLA (61%) > AptB (54%) > Mgn690 (29%) and Cpt1041 (15%). Mean concentrations of MCs, Apts, and Cpts into two drinking water intakes were 3.9 ±â€¯4.7, 0.14 ±â€¯0.21, and 0.38 ±â€¯0.92, respectively. Mean concentrations in surface water were significantly higher (p < 0.05) than in drinking water intakes for MCs but not for Cpts and Apts. Temporal trends in MCs, Cpts, and Apts in the two raw drinking water intakes were significantly correlated (p < 0.05) with measures of cell abundance (chlorophyll-a, Microcystis cell density), UV absorbance, and turbidity in surface water. This study expands current information about cyanobacterial TBPs that occur in lakes and that enter drinking water treatment plants and underscores the need to determine the fate of less studied cyanobacterial metabolites during drinking water treatment that may exacerbate toxicity of more well-known cyanobacterial toxins.

Variable Cyanobacterial Toxin and Metabolite Profiles across Six Eutrophic Lakes of Differing Physiochemical Characteristics.

Future sustainability of freshwater resources is seriously threatened due to the presence  of  harmful  cyanobacterial  blooms,  and  yet,  the  number,  extent,  and  distribution  of  most  cyanobacterial toxins-including "emerging" toxins and other bioactive compounds-are poorly  understood.  We  measured  15  cyanobacterial  compounds-including  four  microcystins  (MC),  saxitoxin (SXT), cylindrospermopsin (CYL), anatoxin-a (ATX) and homo-anatoxin-a (hATX), two  anabaenopeptins (Apt), three cyanopeptolins (Cpt), microginin (Mgn), and nodularin (NOD)-in  six freshwater lakes that regularly experience noxious cHABs. MC, a human liver toxin, was present  in all six lakes and was detected in 80% of all samples. Similarly, Apt, Cpt, and Mgn were detected  in all lakes in roughly 86%, 50%, and 35% of all samples, respectively. Despite being a notable  brackish  water  toxin,  NOD  was  detected  in  the  two  shallowest  lakes-Wingra  (4.3  m)  and  Koshkonong (2.1 m). All compounds were highly variable temporally, and spatially. Metabolite  profiles were significantly different between lakes suggesting lake characteristics influenced the  cyanobacterial community and/or metabolite production. Understanding how cyanobacterial toxins  are  distributed  across  eutrophic  lakes  may  shed  light  onto  the  ecological  function  of  these  metabolites, provide valuable information for their remediation and removal, and aid in the  protection of public health.

Freshwater harmful algal blooms: toxins and children's health.

Massive accumulations of cyanobacteria (a.k.a. "blue-green algae"), known as freshwater harmful algal blooms (FHABs), are a common global occurrence in water bodies used for recreational purposes and drinking water purification. Bloom prevalence is increased due to anthropogenic changes in land use, agricultural activity, and climate change. These photosynthetic bacteria produce a range of toxic secondary metabolites that affect animals and humans at both chronic and acute dosages. Children are especially at risk because of their lower body weight, behavior, and toxic effects on development. Here we review common FHAB toxins, related clinical symptoms, acceptable concentrations in drinking water, case studies of children's and young adults' exposures to FHAB toxins through drinking water and food, methods of environmental and clinical detection in potential cases of intoxication, and best practices for FHAB prevention.