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

Abstract

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). Fortynine of the 197 brominated formulas have not been previously reported. We also were able to tentatively assign possible structures to the formula C 3 HBr 3 N 2 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.

Development and Application of High-Precision Algorithm for Non-Target Identification of Organohalogens Based on Ultrahigh-Resolution Mass Spectrometry

“…The previous study also indicated that Br-DBPs formation is strongly related to bromide concentrations in waters to be disinfected 46 . In contrast to the predominant formation of Cl-DBPs during chlorination of river and reservoir waters typically containing low levels of bromide, Br-DBPs formation is reported to dominate for the other types of environmental waters such as groundwater and coastal seawater containing relatively high Br concentrations 17,18,28 . Disinfection treatment of waters containing high level of bromide (e.g.…”

“…These results suggest that the formation of Cl-DOM adducts is controlled not only by the presence of remaining Cl -, but also by the types of DOM. In order to avoid adduct formation, formic acid has been suggested in the SPE extraction instead of HCl [16][17][18]27,28 . However, the employment of other type of acid, formic acid, in SPE extraction (instead of HCl) may lead to the occurrence of formate adduct ions in ESI negative mode [29][30][31] , interfering the formula assignment of nonhalogenated DOM molecules.…”

“…In contrast to the library-based methods, the SIRIUS software (widely used for metabolites identification) utilizes isotopic patterns to filter multiple potential solutions for the given mass to only a few candidates, and directly determine the X-DBPs with multiple Cl or Br atoms 19 . However, monohalogen formulae (i.e., containing sole Cl or Br) as well as Cl-Br-DBPs are not incorporated in SIRIUS, regardless of their frequent observation in chlorinated samples [3][4][5]17,19,20 . The compatibility of this biomolecule-customized SIRIUS to identify X-DBPs molecules therefore needs to be investigated.…”

“…chlorinated X-DBPs [Cl-DBPs], brominated X-DBPs [Br-DBPs], and Cl-and Br-containing X-DBPs [Cl-Br-DBPs]) is a distinctive signal in organohalogens detection with high levels of confidence. In the past two decades, therefore, isotopic patterns had been successfully employed to selectively detect X-DBPs 5 peaks from UHR-MS spectra 10,11 as well as to identify the X-DBPs and other organic pollutants 2,[12][13][14][15][16][17][18] , non-halogenated metabolites 19 and some unknown biomolecules 20 .…”

Ecological impacts of ballast water loading and discharge: insight into the toxicity and accumulation of disinfection by-products

“…Chlorination achieved 75%–99% efficiency in removing various organisms in ballast water ( Ichikawa et al., 1992 ; Bolch and Hallegraeff, 1993 ; Gray et al., 2006 ), electrochemical treatments had plankton removal efficiency >99% ( Dang et al., 2003 ; Jang et al., 2020 ), oxidation with various oxidants removed 97%–99% of various organisms ( Wright et al., 2007 ; de Lafontaine et al., 2008 ), and ozonation may remove up to 99% of various organisms in ballast water ( Oemcke and Van Leeuwen, 2005 ; Perrins et al., 2006 ). Despite their great and reliable efficiencies, a concern was raised due to the environmental effect caused by the application of disinfection, known as DBPs ( Delacroix et al., 2013 ; Shah et al., 2015 ; Ziegler et al., 2019 ). These chemicals are the results of the used reagent with natural characteristics of water ( Ziegler et al., 2019 ) or originated from the reactions between total residual oxidants (TRO) and the dead organisms in storage during voyage ( Jang and Cha, 2020 ).…”