Types and Distribution of Bioactive Polyunsaturated Aldehydes in a Gradient from Mesotrophic to Oligotrophic Waters in the Alborán Sea (Western Mediterranean).

Polyunsaturated aldehydes (PUAs) are bioactive molecules suggested as chemical defenses and infochemicals. In marine coastal habitats, diatoms reach high PUA production levels during bloom episodes. Two fractions of PUA can usually be analyzed: pPUA obtained via artificial breakage of collected phytoplankton cells and dissolved PUA already released to the environment (dPUA). In nature, resource supply arises as a main environmental controlling factor of PUA production. In this work, we monitored the vertical distribution and daily variation of pPUA associated with large-size phytoplankton and dPUA, at three sites located in the Alborán Sea from mesotrophic to oligotrophic waters. The results corroborate the presence of large-size PUA producers in oligotrophic and mesotrophic waters with a significant (58%-85%) diatom biomass. In addition to diatoms, significant correlations between pPUA production and dinoflagellate and silicoflagellate abundance were observed. 2E,4E/Z-Heptadienal was the most abundant aldehyde at the three sites with higher values (17.1 fg·cell-1) at the most oligotrophic site. 2E,4E/Z-Decadienal was the least abundant aldehyde, decreasing toward the oligotrophic site. For the first time, we describe the daily fluctuation of pPUA attributable to cellular physiological state and not exclusively to taxonomical composition. Our results demonstrate the persistence of threshold levels of dPUA deep in the water column, as well as the different chromatographic profiles of dPUA compared with pPUA. We propose different isomerization processes that alter the chemical structure of the released PUAs with unknown effects on their stability, biological function, and potential bioactivity.

Inactivation of the waterborne marine pathogen Vibrio alginolyticus by photo-chemical processes driven by UV-A, UV-B, or UV-C LED combined with H2O2 or HSO5.

Ultraviolet (UV) radiation is a well-implemented process for water disinfection. The development of emergent UV sources, such as light-emitting diodes (LEDs), has afforded new possibilities for advanced oxidation processes. The emission wavelength is considered to be an important factor for photo-chemical processes in terms of both biological damage and energetic efficiency, as the inactivation mechanisms and mode-of-action may differ according to the wavelength that is applied. In addition, these processes merit exploration for inactivating emerging pathogens, such as marine vibrios, that are important bacteria to control in maritime activities. The main goal of this study was to compare the disinfection efficacy of several UV-LED driven processes with different modes of action. First, the effect of UV-LEDs was assessed at different UV ranges (UV-A, UV-B, or UV-C). Second, the possible enhancement of a combination with hydrogen peroxide (H2O2) or peroxymonosulfate salt (HSO5-) was investigated under two different application strategies, i.e. simultaneous or sequential. The results obtained indicate a high sensitivity of Vibrio alginolyticus to UV radiation, especially under UV-B (kobs = 0.24 cm2/mJ) and UV-C (kobs = 1.47 cm2/mJ) irradiation. The highest inactivation rate constants were obtained for UV/HSO5- (kobs (cm2/mJ)=0.0007 (UV-A); 0.39 (UV-B); 1.79 (UV-C)) with respect to UV/H2O2 (kobs (cm2/mJ)=0.0006 (UV-A); 0.26 (UV-B); and 1.54 (UV-C)) processes, however, regrowth was avoided only with UV/H2O2. Additionally, the disinfection enhancement caused by a chemical addition was more evident in the order UV-A > UV-B > UV-C. By applying H2O2 (10 mg/L) or HSO5- (2.5 mg/L) in a sequential mode before the UV, negligible effects were obtained in comparison with the simultaneous application. Finally, promising electrical energy per order (EEO) values were obtained as follows: UV/HSO5- (EEO (kWh/m3)=1.68 (UV-A); 0.20 (UV-B); 0.04 (UV-C)) and UV/H2O2 (EEO (kWh/m3)=2.15 (UV-A); 0.32 (UV-B); 0.04 (UV-C)), demonstrating the potential of UV-LEDs for disinfection in particular activities such as the aquaculture industry or maritime transport.

Evaluation of algaecide effectiveness of five different oxidants applied on harmful phytoplankton.

Harmful algal blooms (HABs) in coastal areas similarly impact both ecosystems and human health. The translocation of phytoplankton species via maritime transport can potentially promote the growth of HABs in coastal systems. Accordingly, ballast water must be disinfected. The main goal of this study is to assess the effectiveness of different emerging biocides, including H2O2, peracetic acid (PAA), peroxymonosulfate (PMS), and peroxydisulfate (PDS). The effectiveness of these biocides is compared with that of conventional chlorination methods. Their effects on two ichthyotoxic microalgae with worldwide distribution, i.e., Prymnesium parvum and Heterosigma akashiwo, are examined. To ensure the prolonged effectiveness of the different reagents, their concentration-response curves for 14 days are constructed and examined. The results suggest a strong but shorter effect by PMS (EC50 = 0.40-1.99 mg·L-1) and PAA (EC50 = 0.32-2.70 mg·L-1), a maintained effect by H2O2 (EC50 = 6.67-7.08 mg·L-1), and a negligible effect by PDS. H. akashiwo indicates higher resistance than P. parvum, except when H2O2 is used. Based on the growth inhibition performance and consumption of the reagents as well as a review of important aspects regarding their application, using H2O2, PAA, or PMS can be a feasible alternative to chlorine-based reagents for inhibiting the growth of harmful phytoplankton.

Semicontinuous and batch ozonation combined with peroxymonosulfate for inactivation of microalgae in ballast water.

The Ballast Water Management Convention (BWMC) establishes limits regarding the permissible number of viable organisms in discharged ballast water. Ozone as a ballast water treatment is interesting because it can be generated in-situ and has strong oxidant power. Additionally, some oxidants can be formed in reaction with seawater, especially brominated compounds, that assist in inactivating microorganisms. The objective of this study is to assess the efficacy of semicontinuous and batch ozonation as well as their combination with peroxymonosulfate salt (PMS) as methods to be used to ensure compliance with regulation D2 of the BWMC using Tetraselmis suecica as a standard microorganism. Growth modeling method was employed to determine the inactivation achieved by the treatments. The results show that ozone is an effective treatment for accomplishing the D2 of the BWMC. Batch ozonation is more efficient than semicontinuous ozonation probably because of the brominated compounds formed during the ozone saturation of the water. The oxidants that are developed during the ozonation of seawater prolong the residual effect of the treatment throughout the days of storage with practically no presence of them in the ballast tanks at 72 h. The addition of the PMS increases the inactivation in the semicontinuous ozonation, but a threshold concentration of ozone is needed to observe the synergistic effect of both oxidants. No increase is associated with the combination of O3 and PMS in the case of batch ozonation.

Evaluation of three photosynthetic species smaller than ten microns as possible standard test organisms of ultraviolet-based ballast water treatment.

The Ballast Water Management Convention (BWMC) establishes limits for viable organisms in discharged ballast water. However, organisms smaller than 10 µm are not considered in this regulation although they represent, in some regions, the majority of the phytoplankton organisms in marine water. The objective in this study is to assess three photosynthetic species smaller than 10 µm as potential standard test organism (STO) in experimentation focused on the inactivating efficacy of ultraviolet treatments (UV). A growth modelling method was employed to determine the reduction of the viable cell concentration under either light or dark post-treatment conditions to evaluate the importance of the photoreactivation. In spite of its moderate growth rate, the high UV resistance in combination with the abundance and worldwide distribution of Synechococcus sp. and the environmental importance of this species constitute important reasons for considering Synechococcus sp. as a valuable STO for ballast water treatment.

Improving the microalgae inactivating efficacy of ultraviolet ballast water treatment in combination with hydrogen peroxide or peroxymonosulfate salt.

Due to the increasing number of ecosystem invasions with the introduction of exogenous species via ballast water, the International Maritime Organization adopted the Ballast Water Convention (BWMC). The BWMC establishes standards for the concentration of viable organisms in a ballast water discharge. Ultraviolet (UV) irradiation is commonly used for treating ballast water; however, regrowth after UV irradiation and other drawbacks have been reported. In this study, improvement in UV treatment with the addition of hydrogen peroxide or peroxymonosulfate salt was investigated using the microalgae Tetraselmis suecica as the target organism. Results reported that each of these reagents added in a concentration of 10 ppm reduced the concentration of initial cells by more than 96%, increased the UV inactivation rate, and enabled reaching greater level of inactivation with the treatment. These improvements imply a reduction of the UV doses required for a consistent compliance with the BWMC standards.

Effect of the length of dark storage following ultraviolet irradiation of Tetraselmis suecica and its implications for ballast water management.

Meeting the recent biological standards established by the Ballast Water Management Convention requires the application of ballast water treatment systems; ultraviolet irradiation is a frequently used option. However, organisms can repair the damage caused by ultraviolet irradiation primarily with photo-repair mechanisms that are dependent on the availability of light. The objective of this study is to quantify the impact of dark storage following ultraviolet irradiation on the viability of the microalgae Tetraselmis suecica. Results showed that one day of dark storage after ultraviolet irradiation enhanced the inactivation rate by 50% with respect to the absence of dark storage and increased up to the 84% with five days of dark storage. These results are consistent with photorepair, mostly in the first two days, prevented in the dark. The dose required to inactivate a determined ratio of organisms was correlated with the length of the dark post-treatment according to an inverse proportional function. This correlation may help to optimize the operation of ultraviolet ballast water treatment systems. Further, the results show that growth assays can detect organisms that are capable of repair after treatment with UV.

Application of persulfate salts for enhancing UV disinfection in marine waters.

Over the years, industrial activities that generate high salinity effluents have been intensifying; this has relevant potential for causing organic and microbiological pollution which damages both human and ocean health. The development of new regulations, such as ballast water convention, encourage the development of treatment systems that can be feasible for treating seawater effluents. Accordingly, an approach based on the UV activation of persulfate salts has been assessed. In this scenario, two different persulfate sources (S2O82- and HSO5-) were evaluated under UV-C irradiation for disinfection purposes. An optimization process was performed with low chemical doses (<1 mM). In order to extensively examine the applicability on seawater, different water matrices were tested as well as different microorganisms including both fecal and marine bacteria. An enhancement of UV-inactivation with the addition of persulfate salts was achieved in all cases, kinetic rate constant has been accelerated by up to 79% in seawater. It implies a UV-dose saving up to 45% to achieve 4-log reductions. Best efficiencies were obtained with [HSO5-] = 0.005 mM and [S2O82-] = 0.5 mM. Higher effectiveness was obtained with the use of HSO5- due to its low stability and interaction with chloride. Also, different responses were obtained according to the specific microorganisms by achieving faster disinfection in Gram-negative than in Gram-positive bacteria, the sensitivity observed was Vibrio spp. > E. coli > E. faecalis ≈ Marine Heterotrophic Bacteria. With an evaluation of regrowth after treatment, greater cell damage was detected with the addition of persulfate salts. The major ability of regrowth for marine bacteria encourages the use of a residual disinfectant after disinfection processes.

UV-based technologies for marine water disinfection and the application to ballast water: Does salinity interfere with disinfection processes?

Water contained on ships is employed in the majority of activities on a vessel; therefore, it is necessary to correctly manage through marine water treatments. Among the main water streams generated on vessels, ballast water appears to be an emerging global challenge (especially on cargo ships) due to the transport of invasive species and the significant impact that the ballast water discharge could have on ecosystems and human activities. To avoid this problem, ballast water treatment must be implemented prior to water discharge in accordance with the upcoming Ballast Water Management Convention. Different UV-based treatments (photolytic: UV-C and UV/H2O2, photocatalytic: UV/TiO2), have been compared for seawater disinfection. E. faecalis is proposed as a biodosimeter organism for UV-based treatments and demonstrates good properties for being considered as a Standard Test Organism for seawater. Inactivation rates by means of the UV-based treatments were obtained using a flow-through UV-reactor. Based on the two variables responses that were studied (kinetic rate constant and UV-Dose reductions), both advanced oxidation processes (UV/H2O2 and photocatalysis) were more effective than UV-C treatment. Evaluation of salinity on the processes suggests different responses according to the treatments: major interference on photocatalysis treatment and minimal impact on UV/H2O2.

Assessment of imaging-in-flow system (FlowCAM) for systematic ballast water management.

Assessing the disinfection of ballast water and its compliance with international standards requires determining the size, viability, and concentration of planktonic organisms. The FlowCAM (Flow Cytometer and Microscope) is an Imaging Flow Cytometry designed to obtain the particle concentration, images, and quantitative morphologic information. The objective in this paper is to establish the basis for transforming the FlowCAM from being a laboratory analyzer into a tool for systematic monitoring of ballast water. The capacity of the FlowCAM was evaluated by analyzing artificial microbeads, phytoplankton monocultures, and real seawater samples. Microbead analyses reported high accuracy and precision in size and concentration measurements. Monoculture analyses showed the effect of disinfection treatments in cell appearance and growth. Low concentration and heterogeneity of particles in real seawater analyses require the comprehensive observation of images by experts. Additionally, some physical characteristics of the device must be improved. The optimization of device configuration enables the quick transferring of files and information between parties involved in ballast water management. FlowCAM may become a feasible technology for this after the device and protocols are adapted.