A pilot study suggests the correspondence between SAR202 bacteria and dissolved organic matter in the late stage of a year-long microcosm incubation.

SAR202 bacteria are abundant in the marine environment and they have been suggested to contribute to the utilization of recalcitrant organic matter (RDOM) within the ocean's biogeochemical cycle. However, this functional role has only been postulated by metagenomic studies. During a one-year microcosm incubation of an open ocean microbial community with lysed Synechococcus and its released DOM, SAR202 became relatively more abundant in the later stage (after day 30) of the incubation. Network analysis illustrated a high degree of negative associations between SAR202 and a unique group of molecular formulae (MFs) in phase 2 (day 30 to 364) of the incubation, which is empirical evidence that SAR202 bacteria are major consumers of the more oxygenated, unsaturated, and higher-molecular-weight MFs. Further investigation of the SAR202-associated MFs suggested that they were potentially secondary products arising from initial heterotrophic activities following the amendment of labile Synechococcus-derived DOM. This pilot study provided a preliminary observation on the correspondence between SAR202 bacteria and more resistant DOM, further supporting the hypothesis that SAR202 bacteria play important roles in the degradation of RDOM and thus the ocean's biogeochemical cycle.

Dearomatization drives complexity generation in freshwater organic matter.

Dissolved organic matter (DOM) is one of the most complex, dynamic and abundant sources of organic carbon, but its chemical reactivity remains uncertain1-3. Greater insights into DOM structural features could facilitate understanding its synthesis, turnover and processing in the global carbon cycle4,5. Here we use complementary multiplicity-edited 13C nuclear magnetic resonance (NMR) spectra to quantify key substructures assembling the carbon skeletons of DOM from four main Amazon rivers and two mid-size Swedish boreal lakes. We find that one type of reaction mechanism, oxidative dearomatization (ODA), widely used in organic synthetic chemistry to create natural product scaffolds6-10, is probably a key driver for generating structural diversity during processing of DOM that are rich in suitable polyphenolic precursor molecules. Our data suggest a high abundance of tetrahedral quaternary carbons bound to one oxygen and three carbon atoms (OCqC3 units). These units are rare in common biomolecules but could be readily produced by ODA of lignin-derived and tannin-derived polyphenols. Tautomerization of (poly)phenols by ODA creates non-planar cyclohexadienones, which are subject to immediate and parallel cycloadditions. This combination leads to a proliferation of structural diversity of DOM compounds from early stages of DOM processing, with an increase in oxygenated aliphatic structures. Overall, we propose that ODA is a key reaction mechanism for complexity acceleration in the processing of DOM molecules, creation of new oxygenated aliphatic molecules and that it could be prevalent in nature.

Evaluating the photochemical reactivity of disinfection byproducts formed during seawater desalination processes.

Reverse osmosis (RO) is widely used for seawater desalination but pre-chlorination of intake water produces halogenated disinfection byproducts (DBPs). The fate and environmental impacts associated with the discharge of DBP-containing RO brine wastewater are unknown. Therefore, to evaluate if photochemistry plays a role in DBP degradation in seawater, we collected samples at a desalination plant, which were desalted and concentrated using two-inline solid phase extraction (SPE) techniques combining reverse-phase polymeric (PPL) and weak anion exchange (WAX) resins. Both filtered water samples and SPE samples (extracts reconstituted in open ocean seawater) were exposed to simulated sunlight in a custom-built flow-through system. Optical property analysis during irradiation experiments did not provide distinguishing features between intake water and RO reject water (brine). Extractable organic bromine (organoBr) concentrations were low in intake water samples (7.8 µg Br L-1) and did not change significantly due to irradiation. OrganoBr concentrations in laboratory-chlorinated raw water were much higher (135 µg Br L-1) and on average decreased by 42 % after 24 h irradiation. However, while organoBr concentrations were highest in RO reject water (473 µg Br L-1), changes in organoBr concentrations in PPL SPE samples after 24 h irradiation were variable, ranging from a 1-46 % loss. Furthermore, most bromine-containing molecular ions identified by high resolution mass spectrometry that were present in RO reject water before irradiation were also found after both 24 h and 50 h exposures. Although only one RO reject water sample was tested in this study, results highlight that hundreds of yet to be identified brominated DBPs in RO reject water could be resistant to photodegradation or phototransform into existing DBPs in the environment. Future work examining the biolability of DBPs in RO reject water, as well as the interplay between photochemical and biological DBP cycling, is warranted.

Distinct Non-conservative Behavior of Dissolved Organic Matter after Mixing Solimões/Negro and Amazon/Tapajós River Waters.

Positive and negative electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry and 1H NMR revealed major compositional and structural changes of dissolved organic matter (DOM) after mixing two sets of river waters in Amazon confluences: the Solimões and Negro Rivers (S + N) and the Amazon and Tapajós Rivers (A + T). We also studied the effects of water mixing ratios and incubation time on the composition and structure of DOM molecules. NMR spectra demonstrated large-scale structural transformations in the case of S + N mixing, with gain of pure and functionalized aliphatic units and loss of all other structures after 1d incubation. A + T mixing resulted in comparatively minor structural alterations, with a major gain of small aliphatic biomolecular binding motifs. Remarkably, structural alterations from mixing to 1d incubation were in essence reversed from 1d to 5d incubation for both S + N and A + T mixing experiments. Heterotrophic bacterial production (HBP) in endmembers S, N, and S + N mixtures remained near 0.03 µgC L-1 h-1, whereas HBP in A, T, and A + T were about five times higher. High rates of dark carbon fixation took place at S + N mixing in particular. In-depth biogeochemical characterization revealed major distinctions between DOM biogeochemical changes and temporal evolution at these key confluence sites within the Amazon basin.

The Predominance of Ammonia-Oxidizing Archaea in an Oceanic Microbial Community Amended with Cyanobacterial Lysate.

When the oligotrophic microbial community was amended with Synechococcus-derived dissolved organic matter (SDOM) and incubated under the dark condition, archaea relative abundance was initially very low but made up more than 60% of the prokaryotic community on day 60, and remained dominant for at least 9 months. The archaeal sequences were dominated by Candidatus Nitrosopumilus, the Group I.1a Thaumarchaeota. The increase of Thaumarchaeota in the dark incubation corresponded to the period of delayed ammonium oxidation upon an initially steady increase in ammonia, supporting the remarkable competency of Thaumarchaeota in energy utilization and fixation of inorganic carbon in the ocean. IMPORTANCE Thaumarchaeota, which are ammonia-oxidizing archaea (AOA), are mainly chemolithoautotrophs that can fix inorganic carbon to produce organic matter in the dark. Their distinctive physiological traits and high abundance in the water column indicate the significant ecological roles they play in the open ocean. In our study, we found predominant Thaumarchaeota in the microbial community amended with cyanobacteria-derived lysate under the dark condition. Furthermore, Thaumarchaeota remained dominant in the microbial community even after 1 year of incubation. Through the ammonification process, dissolved organic matter (DOM) from cyanobacterial lysate was converted to ammonium which was used as an energy source for Thaumarchaeota to fix inorganic carbon into biomass. Our study further advocates the important roles of Thaumarchaeota in the ocean's biogeochemical cycle.

Comprehensive assessment of dissolved organic matter processing in the Amazon River and its major tributaries revealed by positive and negative electrospray mass spectrometry and NMR spectroscopy.

Rivers are natural biogeochemical systems shaping the fates of dissolved organic matter (DOM) from leaving soils to reaching the oceans. This study focuses on Amazon basin DOM processing employing negative and positive electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI[±] FT-ICR MS) and nuclear magnetic resonance spectroscopy (NMR) to reveal effects of major processes on the compositional space and structural characteristics of black, white and clear water systems. These include non-conservative mixing at the confluences of (1) Solimões and the Negro River, (2) the Amazon River and the Madeira River, and (3) in-stream processing of Amazon River DOM between the Madeira River and the Tapajós River. The Negro River (black water) supplies more highly oxygenated and high molecular weight compounds, whereas the Solimões and Madeira Rivers (white water) contribute more CHNO and CHOS molecules to the Amazon River main stem. Aliphatic CHO and abundant CHNO compounds prevail in Tapajos River DOM (clear water), likely originating from primary production. Sorption onto particles and heterotrophic microbial degradation are probably the principal mechanisms for the observed changes in DOM composition in the Amazon River and its tributaries.

New Perspectives on the Marine Carbon Cycle-The Marine Dissolved Organic Matter Reactivity Continuum.

This perspective challenges our current understanding of the marine carbon cycle, including an alternative explanation of bulk 14C-DOM measurements. We propose the adoption of the carbon reactivity continuum concept previously established for lakes and sediments for the oceans using kinetic data and term this the marine DOM reactivity continuum. We need to gain a fundamental understanding of the biogeochemical drivers of surface water DOM concentrations and reactivity, biological carbon pump efficiency, and the autotrophic communities that are the ultimate but variable sources of marine DOM. This perspective is intended to shift our focus to a more inclusive kinetic model and may lead us to a more accurate assessment of the active and dynamic role marine DOM plays in the global carbon cycle. Currently, the kinetic data to establish and validate such a marine DOM reactivity continuum model are still lacking, and their resolution depends on the discovery of new organic tracers that span large differences in reactivity and microbial degradation rates. We may need to refocus our efforts in deciphering the structure and reactivity of marine organic molecules in a kinetic context, including the microbial and physicochemical constraints on molecular reactivity that are present in the deep ocean.

Biodegradation of Terrigenous Organic Matter in a Stratified Large-Volume Water Column: Implications of the Removal of Terrigenous Organic Matter in the Coastal Ocean.

Large amounts of terrigenous organic matter (TOM) are delivered to the ocean every year. However, removal processes of TOM in the ocean are still poorly constrained. Here, we report results from a 339-day dark incubation experiment with a unique system holding a vertically stratified freshwater-seawater column. The quality and quantity of dissolved organic matter (DOM), RNA-based size-fraction microbial communities, and environmental factors were high-frequency-monitored. Microbial processes impacted TOM composition, including an increased DOM photobleaching rate with incubation time. The mixed layer had changed the bacterial community structure, diversity, and higher oxygen consumption rate. A two-end member modeling analysis suggested that estimated nutrient concentrations and prokaryotic abundance were lower, and total dissolved organic carbon was higher than that of the measured values. These results imply that DOM biodegradation was stimulated during freshwater-seawater mixing. In the bottom layer, fluorescent DOM components increased with the incubation time and were significantly positively related to highly unsaturated, oxygenated, and presumably aromatic compound molecular formulas. These results suggest that surfaced-derived TOM sinking leads to increased DOM transformation and likely results in carbon storage in the bottom water. Overall, these results suggest that microbial transforming TOM plays more important biogeochemical roles in estuaries and coastal oceans than what we know before.

Heterogeneous viral contribution to dissolved organic matter processing in a long-term macrocosm experiment.

Viruses saturate environments throughout the world and play key roles in microbial food webs, yet how viral activities affect dissolved organic matter (DOM) processing in natural environments remains elusive. We established a large-scale long-term macrocosm experiment to explore viral dynamics and their potential impacts on microbial mortality and DOM quantity and quality in starved and stratified ecosystems. High viral infection dynamics and the virus-induced cell lysis (6.23-64.68% d-1) was found in the starved seawater macrocosm, which contributed to a significant transformation of microbial biomass into DOM (0.72-5.32 µg L-1 d-1). In the stratified macrocosm, a substantial amount of viral lysate DOM (2.43-17.87 µg L-1 d-1) was released into the upper riverine water, and viral lysis and DOM release (0.35-5.75 µg L-1 d-1) were reduced in the mixed water layer between riverine water and seawater. Viral lysis was stimulated at the bottom of stratified macrocosm, potentially fueled by the sinking of particulate organic carbon. Significant positive and negative associations between lytic viral production and different fluorescent DOM components were found in the starved and stratified macrocosm, indicating the potentially complex viral impacts on the production and utilization of DOM. Results also revealed the significant viral contribution to pools of both relatively higher molecular weight labile DOM and lower molecular weight recalcitrant DOM. Our study suggests that viruses have heterogeneous impact on the cycling and fate of DOM in aquatic environments.

Acute toxicity of the UV filter oxybenzone to the coral Galaxea fascicularis.

Coral reefs are impacted by a variety of anthropogenic stressors including inputs of chemical contaminants. Although data is currently limited, sunscreens containing ultraviolet (UV) filters have recently been suggested as an emerging class of chemical contaminants. To provide further data on the toxicity of the UV filter oxybenzone (benzophenone-3 or BP-3) to corals, we conducted three independent acute toxicity tests exposing the colonial stony coral Galaxea fascicularis to BP-3 (0.31 to 10 mg/L nominal concentrations). Assessments included daily analytical verification of the exposure concentrations, calculation of the lethal concentration to result in 50% mortality (LC50) and numerous biological endpoints to further investigate the potential impact to both the coral and symbiont. LC50s for the three tests were similar and averaged 6.53 ± 0.47 mg/L nominal concentration BP-3 (4.45 mg/L measured dissolved BP-3). BP-3 did not initiate coral bleaching or show a significant loss of symbionts from the coral tissue in this species as reductions in measurements used for bleaching (i.e. visual color, color saturation and photosynthetic pigment concentrations) were only seen concurrently with tissue loss (i.e. at ≥2.5 mg/L nominal concentration BP-3). Polyp retraction, the most sensitive endpoint of this test, was seen to be a sub-lethal behavioral response to BP-3 exposure. Using the calculated LC50 with measured concentrations from a high-quality UV filter monitoring study in Hawaii, a preliminary, conservative risk quotient for BP-3 was calculated at 0.032. These results suggest that BP-3 likely does not pose an acute risk of mortality to G. fascicularis and additional testing is required to determine sublethal impacts of BP-3 under environmentally relevant concentrations and longer-term chronic exposures. This study highlights complications in conducting toxicity tests with organic UV filters including under-estimations of exposure concentrations and provides recommendations to improve these methods for better comparisons between studies.

Correspondence between DOM molecules and microbial community in a subtropical coastal estuary on a spatiotemporal scale.

Dissolved organic matter (DOM) changes in quantity and quality over time and space, especially in highly dynamic coastal estuaries. Bacterioplankton usually display seasonal and spatial variations in abundance and composition in the coastal regions, and influence the DOM pool via assimilation, transformation and release of organic molecules. The change in DOM can also affect the composition of bacterial community. However, little is known on the correspondence between DOM molecules and bacterial composition, particularly through a systematic field survey. In this study, the spatiotemporal signatures of microbial communities and DOM composition in the subtropical coastal estuary of Xiamen are investigated over one and half years. The co-occurrence analysis between bacteria and DOM suggested microorganisms likely transformed the DOM from a relatively high (>400 Da) to a low (<400 Da) molecular weight, corresponding to an apparent increase in overall aromaticity. This might be the reason why microbial transformation renders "dark" organic matter visible in mass spectrometry due to more efficient ionization of microbial metabolites, as well as photodegradation processes. K- and r-strategists exhibited different correlations with two-size categories of DOM molecules owing to their different lifestyles and responses to environmental nutrient conditions. A comparison of the environmental variables and DOM composition with the microbial communities showed that the environmental/DOM variations played a more important role in shaping the microbial communities than vice versa. This study sheds light on the interactions between microbial populations and DOM molecules at the spatiotemporal scale, improving our understanding of microbial roles in marine biogeochemical cycles.

Combined fluorescent measurements, parallel factor analysis and GC-mass spectrometry in evaluating the photodegradation of PAHS in freshwater systems.

To better understand the transformation and photochemical fate of PAHs in aquatic environments, a custom-designed closed-circuit recirculation photodegradation system, combined with inline semi-continuous fluorescence and absorbance measurements, as well as modelling of excitation-emission (EEM) measurements with parallel factor analysis (PARAFAC), and GC-MS analysis, were combined to create a robust tool for holistically assessing the photodegradation of individual PAHs, their mixtures and photoproduct formation. Selected compounds included in the US EPA priority list, representing 2- to 6-ring compounds, were monitored individually and in mixtures, during 24 h photodegradation experiments. Experiments were conducted in solutions simulating ideal (ultrapure water) and environmentally relevant conditions (1.00 mg L-1 Suwannee River Natural Organic Matter (SRNOM)). The fluorescence, primary PARAFAC components and quantification data obtained by GC-MS, indicated that the decline in parent molecule concentration occurred rapidly within 200 min. The degradation rates of parent PAHs increased with aromaticity (6-ring ≫ 2-ring PAHs) and followed pseudo-first order degradation kinetics. The presence and transformation of degradation products, were captured by PARAFAC. NOM influenced the diversity of photoproducts. From the GC-MS results, photoproducts were only detected in Ant, BAnt and the PAH mixture solutions, but optical property analyses indicated that diverse changes occurred with all PAHs. Spectrometric and chromatographic data demonstrated that parent PAHs and photoproducts co-existed at various stages, which is significant for freshwater systems contaminated with these compounds if photoproducts have higher-toxic potential. These results may be used to model the hazard-potential associated with PAHs present in freshwater systems and understanding the mechanisms that govern their environmental fate.

Unraveling the chemodiversity of halogenated disinfection by-products formed during drinking water treatment using target and non-target screening tools.

To date, there is no analytical approach available that allows the full identification and characterization of highly complex disinfection by-product (DBP) mixtures. This study aimed at investigating the chemodiversity of drinking water halogenated DBPs using diverse analytical tools: measurement of adsorbable organic halogen (AOX) and mass spectrometry (MS)-based target and non-target analytical workflows. Water was sampled before and after chemical disinfection (chlorine or chloramine) at four drinking water treatment plants in Sweden. The target analysis had the highest sensitivity, although it could only partially explain the AOX formed in the disinfected waters. Non-target Fourier transform ion cyclotron resonance (FT-ICR) MS analysis indicated that only up to 19 Cl and/or Br-CHO formulae were common to all disinfected waters. Unexpectedly, a high diversity of halogenated DBPs (presumed halogenated polyphenolic and highly unsaturated compounds) was found in chloraminated surface water, comparable to that found in chlorinated surface water. Overall, up to 86 DBPs (including isobaric species) were tentatively identified using liquid chromatography (LC)-Orbitrap MS. Although further work is needed to confirm their identity and assess their relevance in terms of toxicity, they can be used to design suspect lists to improve the characterization of disinfected water halogenated mixtures.

Influence of the UV/H2O2 Advanced Oxidation Process on Dissolved Organic Matter and the Connection between Elemental Composition and Disinfection Byproduct Formation.

The UV/H2O2 process is a promising advanced oxidation process (AOP) for micropollutant abatement in drinking water treatment and water reuse plants. However, during micropollutant degradation by the AOP, dissolved organic matter (DOM) and the disinfection byproduct (DBP) formation potential may also be altered. This study investigated the influence of the UV/H2O2 AOP on the elemental composition and DBP formation potential of two DOM isolates by using ultrahigh-resolution mass spectrometry (UHRMS). After the AOP, 629 new chemical formulas with an increased degree of oxidation and decreased aromaticity were obtained. Such alterations led to the formation of 226 unknown DBPs with decreased aromaticity indices (AImod) in the subsequent 3-day chlorination. Links between the unknown DBPs and the corresponding precursors in DOM were visualized by network computational analysis. The analysis gave three zones in the van Krevelen diagram based on the possibility of the C7-22HnOm formulas located in each zone to link to the corresponding DBPs. A further investigation with two model compounds reconfirmed the hydroxylation and ring cleavage of DOM by HO· attack during the AOP and the influence on DBP formation. These results obtained from UHRMS build the connection between the elemental composition of DOM and the formation potential of DBPs.

Advanced identification of global bioactivity hotspots via screening of the metabolic fingerprint of entire ecosystems.

Natural products (NP) are a valuable drug resource. However, NP-inspired drug leads are declining, among other reasons due to high re-discovery rates. We developed a conceptual framework using the metabolic fingerprint of entire ecosystems (MeE) to facilitate the discovery of global bioactivity hotspots. We assessed the MeE of 305 sites of diverse aquatic ecosystems, worldwide. All samples were tested for antiviral effects against the human immunodeficiency virus (HIV), followed by a comprehensive screening for cell-modulatory activity by High-Content Screening (HCS). We discovered a very strong HIV-1 inhibition mainly in samples taken from fjords with a strong terrestrial input. Multivariate data integration demonstrated an association of a set of polyphenols with specific biological alterations (endoplasmic reticulum, lysosomes, and NFkB) caused by these samples. Moreover, we found strong HIV-1 inhibition in one unrelated oceanic sample closely matching to HIV-1-inhibitory drugs on a cytological and a chemical level. Taken together, we demonstrate that even without physical purification, a sophisticated strategy of differential filtering, correlation analysis, and multivariate statistics can be employed to guide chemical analysis, to improve de-replication, and to identify ecosystems with promising characteristics as sources for NP discovery.

Contribution of ketone/aldehyde-containing compounds to the composition and optical properties of Suwannee River fulvic acid revealed by ultrahigh resolution mass spectrometry and deuterium labeling.

A prior method of mass labeling ketone-/aldehyde-containing species in natural dissolved organic matter (DOM) is further developed and applied. This application involved the treatment of Suwannee River fulvic acid (SRFA) with increasing concentrations of sodium borodeuteride (NaBD4), followed by detection of reduced species via negative mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR MS). The extent of reduction, as determined by ESI FTICR MS, resulting from increasing concentrations of NaBD4 correlated well with changes in the absorption and emission spectra of the corresponding untreated and borodeuteride-reduced samples, providing evidence that ketone/aldehyde functional groups contribute substantially to the bulk optical properties of SRFA. Furthermore, the differences in the reactivity and abundance of ketone-/aldehyde-containing species for various regions in Van Krevelen plots were revealed, thus showing how this mass labeling method can be used to provide more detailed structural information about components within complex DOM samples than that provided by the determination and analysis of molecular formulae alone. Graphical abstract.

Molecular differences between water column and sediment pore water SPE-DOM in ten Swedish boreal lakes.

Boreal lakes are considered hot spots of dissolved organic matter (DOM) processing within the global carbon cycle. This study has used FT-ICR mass spectrometry and comprehensive data evaluation to assess the molecular differences of SPE-DOM between lake column water SPE-DOM and sedimentary pore water SPE-DOM in 10 Swedish boreal lakes of the Malingsbo area, which were selected for their large diversity of physicochemical and morphological characteristics. While lake column water is well mixed and fairly oxygenated, sedimentary pore water is subject to depletion of oxygen and to confinement of molecules. Robust trends were deduced from molecular compositions present in all compartments and in all 10 lakes ("common compositions") with recognition of relative abundance. Sedimentary pore water SPE-DOM featured higher proportions of heteroatoms N and S, higher average H/C ratios in presence of higher DBE/C ratios, and higher average oxygenation than lake column water SPE-DOM. These trends were observed in all lakes except Ljustjärn, which is a ground water fed kettle lake with an unique lake biogeochemistry. Analogous trends were also observed in case of single or a few lakes and operated also for compounds present solely in either lake column water or sedimentary pore water. Unique compounds detected in either compartments and/or in a few lakes showed higher molecular diversity than the "common compositions". Processing of DOM molecules in sediments included selective preservation for polyphenolic compounds and microbial resynthesis of selected molecules of considerable diversity.

Simulated Sunlight Selectively Modifies Maillard Reaction Products in a Wide Array of Chemical Reactions.

The photochemical transformation of Maillard reaction products (MRPs) under simulated sunlight into mostly unexplored photoproducts is reported herein. Non-enzymatic glycation of amino acids leads to a heterogeneous class of intermediates with extreme chemical diversity, which is of particular relevance in processed and stored food products as well as in diabetic and age-related protein damage. Here, three amino acids (lysine, arginine, and histidine) were reacted with ribose at 100 °C in water for ten hours. Exposing these model systems to simulated sunlight led to a fast decay of MRPs. The photodegradation of MRPs and the formation of new compounds have been studied by fluorescence spectroscopy and nontargeted (ultra)high-resolution mass spectrometry. Photoreactions showed strong selectivity towards the degradation of electron-rich aromatic heterocycles, such as pyrroles and pyrimidines. The data show that oxidative cleavage mechanisms dominate the formation of photoproducts. The photochemical transformations differed fundamentally from "traditional" thermal Maillard reactions and indicated a high amino acid specificity.

Formation of Brominated Organic Compounds and Molecular Transformations in Dissolved Organic Matter (DOM) after Ballast Water Treatment with Sodium Dichloroisocyanurate Dihydrate (DICD).

Estuarine water treated with a ballast water management system (BWMS) using a solution of dissolved dichloroisocyanurate dihydrate (DICD) resulted in the formation of newly described brominated disinfection byproducts (Br-DBPs). Analysis of dissolved organic matter (DOM) in untreated water with ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) identified 3897 m/z ions and their exact molecular formulas. After DICD treatment, a total of 213 halogenated molecular ions with relative abundance of at least 1% were assigned and confirmed using isotope simulation. Halogenated ions were assigned in four DBP elemental groups including CHOBr (180), CHONBr (13), CHOCl (16), and CHOBrCl (4). Forty-nine of the 197 brominated formulas have not been previously reported. We also were able to tentatively assign possible structures to the formula C3HBr3N2 due to very limited isomeric possibilities. The tentatively assigned compound found at 6.4% relative abundance was identified as either tribromoimidazole or tribromopyrazole. Our results show the formation of complex halogenated DBPs that are formed in the treatment of water with a novel BWMS that employs granular DICD as a biocide. The toxicological and mutagenic properties as well as the fate of these newly identified brominated DBPs are unknown.

Microbial transformation of virus-induced dissolved organic matter from picocyanobacteria: coupling of bacterial diversity and DOM chemodiversity.

Picocyanobacteria make up half of the ocean's primary production, and they are subjected to frequent viral infection. Viral lysis of picocyanobacteria is a major driving force converting biologically fixed carbon into dissolved organic carbon (DOC). Viral-induced dissolved organic matter (vDOM) released from picocyanobacteria provides complex organic matter to bacterioplankton in the marine ecosystem. In order to understand how picocyanobacterial vDOM are transformed by bacteria and the impact of this process on bacterial community structure, viral lysate of picocyanobacteria was incubated with coastal seawater for 90 days. The transformation of vDOM was analyzed by ultrahigh-resolution mass spectrometry and the shift of bacterial populations analyzed using high-throughput sequencing technology. Addition of picocyanobacterial vDOM introduced abundant nitrogen components into the coastal water, which were largely degraded during the 90 days' incubation period. However, some DOM signatures were accumulated and the total assigned formulae number increased over time. In contrast to the control (no addition of vDOM), bacterial community enriched with vDOM changed markedly with increased biodiversity indices. The network analysis showed that key bacterial species formed complex relationship with vDOM components, suggesting the potential correspondence between bacterial populations and DOM molecules. We demonstrate that coastal bacterioplankton are able to quickly utilize and transform lysis products of picocyanobacteria, meanwhile, bacterial community varies with changing chemodiverisity of DOM. vDOM released from picocyanobacteria generated a complex labile DOM pool, which was converted to a rather stable DOM pool after microbial processing in the time frame of days to weeks.