Thomas Höfer

Emerging risks from ballast water treatment: The run-up to the International Ballast Water Management Convention

Uptake and discharge of ballast water by ocean-going ships contribute to the worldwide spread of aquatic invasive species, with negative impacts on the environment, economies, and public health. The International Ballast Water Management Convention aims at a global answer. The agreed standards for ballast water discharge will require ballast water treatment. Systems based on various physical and/or chemical methods were developed for on-board installation and approved by the International Maritime Organization. Most common are combinations of high-performance filters with oxidizing chemicals or UV radiation. A well-known problem of oxidative water treatment is the formation of disinfection by-products, many of which show genotoxicity, carcinogenicity, or other long-term toxicity. In natural biota, genetic damages can affect reproductive success and ultimately impact biodiversity. The future exposure towards chemicals from ballast water treatment can only be estimated, based on land-based testing of treatment systems, mathematical models, and exposure scenarios. Systematic studies on the chemistry of oxidants in seawater are lacking, as are data about the background levels of disinfection by-products in the oceans and strategies for monitoring future developments. The international approval procedure of ballast water treatment systems compares the estimated exposure levels of individual substances with their experimental toxicity. While well established in many substance regulations, this approach is also criticised for its simplification, which may disregard critical aspects such as multiple exposures and long-term sub-lethal effects. Moreover, a truly holistic sustainability assessment would need to take into account factors beyond chemical hazards, e.g. energy consumption, air pollution or waste generation.

Regulatory toxicology in the twenty-first century: challenges, perspectives and possible solutions

Abstract The advent of new testing systems and “omics”-technologies has left regulatory toxicology facing one of the biggest challenges for decades. That is the question whether and how these methods can be used for regulatory purposes. The new methods undoubtedly enable regulators to address important open questions of toxicology such as species-specific toxicity, mixture toxicity, low-dose effects, endocrine effects or nanotoxicology, while promising faster and more efficient toxicity testing with the use of less animals. Consequently, the respective assays, methods and testing strategies are subject of several research programs worldwide. On the other hand, the practical application of such tests for regulatory purposes is a matter of ongoing debate. This document summarizes key aspects of this debate in the light of the European “regulatory status quo”, while elucidating new perspectives for regulatory toxicity testing.

Peracetic Acid Oxidation of Saline Waters in the Absence and Presence of H2O2: Secondary Oxidant and Disinfection Byproduct Formation

Peracetic acid (PAA) is a disinfectant considered for use in ballast water treatment, but its chemical behavior in such systems (i.e., saline waters) is largely unknown. In this study, the reactivity of PAA with halide ions (chloride and bromide) to form secondary oxidants (HOCl, HOBr) was investigated. For the PAA-chloride and PAA-bromide reactions, second-order rate constants of (1.47 ± 0.58) × 10(-5) and 0.24 ± 0.02 M(-1) s(-1) were determined for the formation of HOCl or HOBr, respectively. Hydrogen peroxide (H2O2), which is always present in PAA solutions, reduced HOCl or HOBr to chloride or bromide, respectively. As a consequence, in PAA-treated solutions with [H2O2] > [PAA], the HOBr (HOCl) steady-state concentrations were low with a limited formation of brominated (chlorinated) disinfection byproducts (DBPs). HOI (formed from the PAA-iodide reaction) affected this process because it can react with H2O2 back to iodide. H2O2 is thus consumed in a catalytic cycle and leads to less efficient HOBr scavenging at even low iodide concentrations (<1 μM). In PAA-treated solutions with [H2O2] < [PAA] and high bromide levels, mostly brominated DBPs are formed. In synthetic water, bromate was formed from the oxidation of bromide. In natural brackish waters, bromoform (CHBr3), bromoacetic acid (MBAA), dibromoacetic acid (DBAA), and tribromoacetic acid (TBAA) formed at up to 260, 106, 230, and 89 μg/L, respectively for doses of 2 mM (ca. 150 mg/L) PAA and [H2O2] < [PAA]. The same brackish waters, treated with PAA with [H2O2] ≫ [PAA], similar to conditions found in commercial PAA solutions, resulted in no trihalomethanes and only low haloacetic acid concentrations.

Assessing the risk of ballast water treatment to human health

Ballast water management systems utilizing noxious chemicals have to be approved according to the Ballast Water Convention by the International Maritime Organization (IMO). The approval procedure requires human health risk assessment. Our objective was to evaluate the existing human health risk assessment process for ballast water management systems. Towards this end, we analyzed the available applications for IMO approval. Since the majority of active substances currently in use are oxidative compounds the corresponding treatment systems generate and release a large number of disinfection by-products. The application dossiers only select a number of by-products for risk assessment. We propose a more comprehensive approach based on the type of ballast water management system, the quality of water treated and the toxicity of compounds discharged into the environment. Subsequent to effects assessment we propose to classify substances according to a hazard evaluation procedure, based on an approach used for maritime transport. We identified a need for better exposure assessment. This requires knowledge of exposure situations. We provide a comprehensive listing of occupational and non-occupational exposure settings and quantification models for exposure assessment.

Offshore experiments on styrene spillage in marine waters for risk assessment

Within the context of risk evaluation of chemical spillages into the marine environment, this paper reports on an offshore experiment to study the behaviour of styrene spilled into sea under natural conditions and discusses theoretical approaches. Floating structures were used to enclose the spillage and the gaseous cloud formation, and dissolution processes were in situ monitored. The identification of spill risks for man and marine environment through GESAMPs hazard profile is described for styrene: Styrene is rated as a chemical with a significant health hazard that will float but also evaporate. However, monitoring of the water column in the experiments showed that the concentration of styrene in water during the first hour represents 50% of the product spilled. For the potentially exposed public, the GESAMP hazard rating recommends the closure of beaches and evacuation. The risk assessment developed from experimental data confirms this safety advice.

Dry bulk cargo shipping — An overlooked threat to the marine environment?

Approximately 9.5billiontonnes of goods is transported over the world oceans annually with dry bulk representing the largest cargo group. This paper aims to analyse whether the transport and associated inputs of dry bulks into the sea create a risk for the marine environment. For this purpose, we analyse the international regulatory background concerning environmental protection (MARPOL), estimate quantities and identify inputs of such cargoes into the oceans (accidental and operational), and use available information for hazard assessment. Annually, more than 2.15milliontonnes of dry bulk cargoes are likely to enter the oceans, of which 100,000tonnes are potentially harmful to the marine environment according to the definition included in draft maritime regulation. The assessment of the threat to the marine environment is hampered by a lack of available information on chemical composition, bioavailability and toxicity. Perspectives for amendments of the unsatisfying pollution prevention regulations are discussed.

The potential for dispersant use as a maritime oil spill response measure in German waters

In case of an oil spill, dispersant application represents a response option, which enhances the natural dispersion of oil and thus reduces coating of seabirds and coastal areas. However, as oil is transferred to the water phase, a trade-off of potential harmful effects shifted to other compartments must be performed. This paper summarizes the results of a workshop on the current knowledge on risks and benefits of the use of dispersants with respect to specific conditions encountered at the German sea areas. The German North Sea coast is a sensitive ecosystem characterised by tidal flats, barrier islands and salt marshes. Many prerequisites for a potential integration of dispersants as spill response option are available in Germany, including sensitivity maps and tools for drift modelling of dispersed and undispersed oil. However, open scientific questions remain concerning the persistence of dispersed oil trapped in the sediments and potential health effects.