Algae impacted drinking water: Does switching to chloramination produce safer drinking water?

Harmful algal (cyanobacterial) blooms (HABs) are increasing throughout the world. HABs can be a direct source of toxins in freshwater sources, and associated algal organic matter (AOM) can act as precursors for the formation of disinfection by-products (DBPs) in drinking water. This study investigated the impacts of algae on DBP formation using treatment with chloramine, which has become a popular disinfectant in the U.

Shoreline Drying of Biomass Can Lead to the Release and Formation of Toxic Saxitoxin Analogues to the Water Column.

The harmful, filamentous cyanobacteria produces several toxic analogues of saxitoxin ( toxins 1-6, or LWTs 1-6), grows in shallow water, and can deposit significant biomass on nearby shorelines. Here, we show that the LWTs are stable in the biomass during subsequent drying but that the process facilitates the later release of LWTs upon return to the water column. Under basic conditions, LWTs hydrolyzed to generate products that were significantly more neurotoxic than the initial toxins.

Growth of the harmful benthic cyanobacterium Microseira wollei is driven by legacy sedimentary phosphorous.

Models for cyanobacterial harmful algae blooms (cHABs) in fresh waters are usually predicated on the relationship between cyanobacterial ecology and dissolved nutrients, particularly phosphorous. Here we show legacy sediment-associated phosphorous as the primary driver of a benthic cHAB, not phosphorous in the water column. Biogeographical surveys by teams of citizen science volunteers working with the University of South Carolina identified over 200 distinct mats of Microseira wollei in Lake Wateree, SC based on toxin characterization.

Microseira wollei and Phormidium algae more than doubles DBP concentrations and calculated toxicity in drinking water.

Warm weather and excess nutrients from agricultural runoff trigger harmful algal blooms, which can affect drinking water safety due to the presence of algal toxins and the formation of disinfection by-products (DBPs) during drinking water treatment. In this study, 66 priority, unregulated and regulated DBPs were quantified in chlorinated controlled laboratory reactions of harmful algae Microseira wollei (formerly known as Lyngbya wollei) and Phormidium using gas chromatography (GC)-mass spectrometry (MS). Live algae samples collected from algae-impacted lakes in South Carolina were chlorinated in both ultrapure water and real source waters containing natural organic matter.

Fe-catalyzed sulfide oxidation in hydrothermal plumes is a source of reactive oxygen species to the ocean.

Historically, the production of reactive oxygen species (ROS) in the ocean has been attributed to photochemical and biochemical reactions. However, hydrothermal vents emit globally significant inventories of reduced Fe and S species that should react rapidly with oxygen in bottom water and serve as a heretofore unmeasured source of ROS. Here, we show that the Fe-catalyzed oxidation of reduced sulfur species in hydrothermal vent plumes in the deep oceans supported the abiotic formation of ROS at concentrations 20 to 100 times higher than the average for photoproduced ROS in surface waters.

Higher intestinal and circulatory lactate associated NOX2 activation leads to an ectopic fibrotic pathology following microcystin co-exposure in murine fatty liver disease.

Clinical studies implicated an increased risk of intestinal fibrosis in patients with nonalcoholic fatty liver disease (NAFLD). Our previous studies have shown that microcystin-LR (MC-LR) exposure led to altered gut microbiome and increased abundance of lactate producing bacteria and intestinal inflammation in underlying NAFLD. This led us to further investigate the effects of the MC-LR, a PP2A inhibitor in activating the TGF-β fibrotic pathway in the intestines that might be mediated by increased lactate induced redox enzyme NOX2.

Emerging Lyngbya wollei toxins: A new high resolution mass spectrometry method to elucidate a potential environmental threat.

Mass spectrometric methods for the quantitative and qualitative analyses of algal biotoxins are often complicated by co-eluting compounds that present analytically as interferences. This issue is particularly critical for organic polyamines, where co-eluting materials can suppress the formation of cations during electrospray ionization. Here we present an extraction procedure designed specifically to overcome matrix-derived ion suppression of algal toxins in samples of Lyngbya wollei, a filamentous benthic algae known to produce several saxitoxin analogues.

Aflatoxin-Exposure of Vibrio gazogenes as a Novel System for the Generation of Aflatoxin Synthesis Inhibitors.

Aflatoxin is a mycotoxin and a secondary metabolite, and the most potent known liver carcinogen that contaminates several important crops, and represents a significant threat to public health and the economy. Available approaches reported thus far have been insufficient to eliminate this threat, and therefore provide the rational to explore novel methods for preventing aflatoxin accumulation in the environment. Many terrestrial plants and microbes that share ecological niches and encounter the aflatoxin producers have the ability to synthesize compounds that inhibit aflatoxin synthesis.

Sediment nickel bioavailability and toxicity to estuarine crustaceans of contrasting bioturbative behaviors--an evaluation of the SEM-AVS paradigm.

Robust sediment quality criteria require chemistry and toxicity data predictive of concentrations where population/community response should occur under known geochemical conditions. Understanding kinetic and geochemical effects on toxicant bioavailability is key, and these are influenced by infaunal sediment bioturbation. This study used fine-scale sediment and porewater measurement of contrasting infaunal effects on carbon-normalized SEM-AVS to evaluate safe or potentially toxic nickel concentrations in a high-binding Spartina saltmarsh sediment (4%TOC; 35-45 μmol-S2-·g(-1)).

Geochemical production of reactive oxygen species from biogeochemically reduced Fe.

The photochemical reduction of Fe(III) complexes to Fe(II) is a well-known initiation step for the production of reactive oxygen species (ROS) in sunlit waters. Here we show a geochemical mechanism for the same in dark environments based on the tidally driven, episodic movement of anoxic groundwaters through oxidized, Fe(III) rich sediments. Sediment samples were collected from the top 5 cm of sediment in a saline tidal creek in the estuary at Murrell's Inlet, South Carolina and characterized with respect to total Fe, acid volatile sulfides, and organic carbon content.

Surface charge controls the fate of Au nanorods in saline estuaries.

This work reports the distribution of negatively charged, gold core nanoparticles in a model marine estuary as a function of time. A single dose of purified polystyrene sulfonate (PSS)-coated gold nanorods was added to a series of three replicate estuarine mesocosms to emulate an abrupt nanoparticle release event to a tidal creek of a Spartina -dominated estuary. The mesocosms contained several phases that were monitored: seawater, natural sediments, mature cordgrass, juvenile northern quahog clam, mud snails, and grass shrimp.

Surface-functionalization effects on uptake of fluorescent polystyrene nanoparticles by model biofilms.

A study was conducted to investigate the role of nanoparticle (NP) surface functionalization/charge on their uptake by biofilms. Biofilms, bacterial colonies attached to surfaces via extracellular polymers, are effective at removing suspended nanomaterials from the aqueous phase. However, the mechanisms regulating particle uptake are unknown.

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Combinatorial parameter space as an empirical tool for predicting water chemistry: Fe(II) oxidation across a watershed.

Fe(II) oxidation kinetics in surface waters are a complex function of the concentration of several dissolved species that vary geographically and temporally across watersheds. This work reports an empirical, combinatorial investigation of Fe(II) oxidation that simultaneously evaluated these variations across the pH, Fe(II), PO₄³⁻, Cl⁻, Br(-), CO₃²⁻, and natural organic matter (NOM) axes. The work assayed the effects of independent and dependent variables through application of a novel experimental design that varied Fe(II), PO₄³⁻, Cl⁻, Br⁻, and CO₃²⁻ along the pH axis.

Short-term Fe cycling during Fe(II) oxidation: exploring joint oxidation and precipitation with a combinatorial system.

The net oxidation of Fe(II)aq by dioxygen initiates a suite of reactions including the oxidation of multiple Fe(II) complexes, generation of secondary oxidants, Fe(III) reduction, and precipitation of insoluble products. This work reports application of a multifactorial strategy to describe the oxidation of Fe(II) under conditions that correspond to those found where Fe(II)-rich groundwaters mix rapidly with overlying oxygenated waters. Response surfaces were constructed describing the relationship of the net oxidation process with mixtures of the common ligands chloride (Cl-), bromide (Br-), total carbonate (CO3(2-)), Fe(II), and Suwannee River natural organic matter (SRNOM) at pH 8.

Reaction of N-acylhomoserine lactones with hydroxyl radicals: rates, products, and effects on signaling activity.

Chemical communication in bacteria, sometimes called quorum sensing, is a fundamental microbial process that is based on the exchange of molecular signals between cells. The signaling molecules involved in this process are thermodynamically unstable in some environments and their degradation affects microbial communication. This work reports the oxidation of a series of substituted N-acylhomoserine lactones (AHLs, a class of quorum sensing signals) by hydroxyl radicals.

Multivariate examination of Fe(II)/Fe(III) cycling and consequent hydroxyl radical generation.

The introduction of Fe(II)(aq) into aerated solutions resulted in net Fe(II) oxidation with concomitant, rapid Fe(II)/Fe(IIII) cycling and concurrent generation of reactive oxygen species. The effect of mixtures of naturally occurring solutes on Fe(II)/Fe(III) cycling and the concurrent oxidation of dissolved organics is reported. The experimental strategy was based on a multivariate, microscale, high-throughput approach for evaluating the effect of covarying concentrations of bromide, iodide, Suwannee River natural organic matter (SRNOM), chloride, and total carbonate species.

Transfer of gold nanoparticles from the water column to the estuarine food web.

Within the next five years the manufacture of large quantities of nanomaterials may lead to unintended contamination of terrestrial and aquatic ecosystems. The unique physical, chemical and electronic properties of nanomaterials allow new modes of interaction with environmental systems that can have unexpected impacts. Here, we show that gold nanorods can readily pass from the water column to the marine food web in three laboratory-constructed estuarine mesocosms containing sea water, sediment, sea grass, microbes, biofilms, snails, clams, shrimp and fish.

Identification of hydroxyl radical oxidation products of N-hexanoyl-homoserine lactone by reversed-phase high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry.

A reversed-phase high-performance liquid chromatography/electrospray tandem mass spectrometry method was developed for the characterization of hydroxyl radical oxidation products of N-hexanoyl-homoserine lactone (C6-HSL), a member of the N-acylhomoserine lactone (AHL) class of microbial quorum-sensing signaling molecules identified in many Gram-negative strains of bacteria. Six products were identified: four with molecular weight (MW) of 213 and two with MW of 260. The characteristic product ions formed through collision-induced dissociation (CID) provided diagnostic structural information.

The adsorption of saxitoxin to clays and sediments in fresh and saline waters.

The adsorption of saxitoxin to Na- and Ca-montmorillonite, kaolin (crystalline and amorphous), kaolinite, Bread and Butter Creek sediment (an estuarine tidal creek), Gulf of Mexico sediment, and Santa Barbara Basin sediment in deionized water and 32 per thousand salinity simulated seawater (Instant Ocean) is reported. Adsorption was partially reversible for all cases and best described using a Freundlich isotherm. The corresponding Freundlich constants (K(F)) ranged from 8.

Use of multiparametric techniques to quantify the effects of naturally occurring ligands on the kinetics of Fe(II) oxidation.

A multifactorial experimental design was employed to quantify and rank the effects of a series of ligands on the rate of Fe(II) (18 microM) oxidation in a system containing chloride, sulfate, carbonate/bicarbonate, fluoride, and natural organic matter (NOM) at pH 8.34 +/- 0.13.

Autoinducers extracted from microbial mats reveal a surprising diversity of N-acylhomoserine lactones (AHLs) and abundance changes that may relate to diel pH.

Microbial mats are highly structured and diverse communities, and one of the earliest-known life assemblages. Mat bacteria interact within an environment marked by strong geochemical gradients and fluctuations. We examined natural mat systems for the presence of autoinducers involved in quorum sensing, a form of cell-cell communication.

Characterization of the Ag mediated surface-enhanced Raman spectroscopy of saxitoxin.

The rapid detection and quantification of saxitoxin (STX) is reported using surface-enhanced Raman spectroscopy (SERS) with a colloidal hydrosol of silver nanoparticles. Under the conditions of our experiments, the limit of detection (LD) for STX using SERS is 3 nM, with a limit of quantification (LQ) of 20 nM. It is shown that the SERS method is rapid, with spectra being collected in as little as 5 seconds total integration time for a 40 nM STX sample.

Gold nanorods as nanoadmicelles: 1-naphthol partitioning into a nanorod-bound surfactant bilayer.

As-prepared gold nanorods, stable in aqueous solution, bear a bilayer of the cationic surfactant cetyltrimethylammonium bromide (CTAB). This bilayer provides a approximately 3 nm thick hydrophobic layer that could be used to sequester hydrophobic organic molecules from aqueous solution. We have investigated the uptake of 1-naphthol as a model hydrophobic compound by CTAB-coated gold nanorods using both ultraviolet-visible spectroscopy and gas chromatography with flame ionization detection.