Full-scale comparison of UV/H2O2 and UV/Cl2 advanced oxidation: The degradation of micropollutant surrogates and the formation of disinfection byproducts.

The photolysis of chlorine by UV light leads to the formation of the hydroxyl radicals (OH) as well as reactive chlorine species (RCS) that can be effective as advanced oxidation processes (AOPs) for water treatment. Much of the research to date has been done at laboratory- or bench-scale. This study reports results from a model that demonstrates that the relative effectiveness of the UV/Cl2 AOP compared to the more traditional UV/H2O2 AOP is a function of optical path length. As such, the relative effectiveness of the two treatment options evaluated at small scale may not reflect the relative performance at full-scale, making results previously obtained at small-scale potentially less scalable. This study therefore compares the performance of UV/Cl2 to UV/H2O2 at a full-scale water treatment plant, using sucralose and caffeine as spiked surrogates for contaminants that are reactive solely to OH radicals, and to both OH and RCS, respectively. pH was varied between 6.5 and 8.0. The results demonstrated that when using a medium pressure UV lamp, UV/Cl2 might lead to approximately twice the production of OH radicals as UV/H2O2 at pH 6.5 when using the same molar oxidant concentration, but adding chlorine to the UV reactor at pH 8.0 had a negligible impact on OH radical concentration in comparison to UV alone. The study also confirmed previous small-scale results that RCS can be a major contributor to UV/Cl2 treatment for compounds such as caffeine that are susceptible to RCS, with UV/Cl2 effective at both pH 6.5 and 8.0 for such compounds. Disinfection byproducts were monitored, with adsorbable organohalide (AOX) formation increasing by approximately 10 µg-Cl/L due to chlorine photolysis, but only at pH 6.5 and not at pH 8.0. This implies that UV/Cl2 might increase AOX mostly due to reaction between OH and organic precursors to make them more reactive with chlorine, and not due to RCS. The formation of specific DBPs of current or emerging regulatory interest was minimal under all conditions, except for chlorate. Chlorate yields were in the order of 6-18% of the photolysed chlorine.

The Biological Basis for Ballast Water Performance Standards: "Viable/Non-Viable" or "Live/Dead"?

The shipping industry is critical to international commerce; however, contemporary shipping practices involve uptake and discharge of ballast water, which introduces the potential for transfer of nonindigenous, invasive species among geographically distinct habitats. To counteract this hazard, regulations for ballast water management have been implemented by the International Maritime Organization (IMO) and by regulatory agencies such as the United States Coast Guard (USCG). IMO and USCG discharge standards are numerically identical, but involve different definitions of treatment end points, which are based on fundamentally different biological assays for quantification of ballast water treatment effectiveness. Available assays for quantification of the responses of organisms in the 10-50 µm size range include vital stains based on fluorescein diacetate (FDA), sometimes used in combination with 5-chloromethylfluorescein diacetate (CMFDA), observations of motility, and the most probable number dilution culture method (MPN). The mechanisms and implications of these assays are discussed relative to the Type Approval process, which quantitatively evaluates compliance with ballast water discharge standards (BWDSs) under controlled shipboard and land-based tests. For antimicrobial processes that accomplish treatment by preventing subsequent replication of the target species, the FDA/CMFDA and MPN methods can yield dramatically different results. An important example of a treatment process that is affected by the choice of assay is ultraviolet (UV) irradiation. Results of laboratory and field experiments have demonstrated UV-based technologies to be effective for accomplishing the objectives of ballast water treatment (inactivation of cellular reproduction), when the MPN assay is used as the basis for evaluation. The FDA, CMFDA, motility, and MPN methods are subject to well recognized sources of error; however, the MPN method is based on a response that is consistent with the objectives of ballast water management as well as the mechanism of action of UV-based inactivation. Complementary assays are available for use in compliance testing; however, the development of relevant indicative tests remains as a research priority. Historical lessons learned from applications of vital stains (and other indirect methods) for quantification of microbial responses to UV irradiation in other settings also support the use of assays that provide a direct measure of growth and reproduction, such as MPN. Collectively, these observations point to the use of MPN assays as the standard for type testing, especially when UV-based treatment is employed.