Metals and suspended solids in the effluents from in-water hull cleaning by remotely operated vehicle (ROV): Concentrations and release rates into the marine environment.

An increase in the use of ROVs for in-water hull cleaning (IWC) has led to the need to understand the risks to the marine environment posed by the release of IWC effluents. The primary objective of this research is to investigate the characteristics of wastewater generated during IWC, specifically concerning suspended solids (SS) and metal concentrations, and their release rates and total load to the environment. The IWC effluents contain substantial amounts of SS and metals, with Cu and Zn being the most prevalent. These metals are predominantly associated with fine antifouling paint particles, posing a potential risk of secondary pollution upon release into the marine environment. While the treatment systems demonstrated effectiveness in reducing SS and particulate metals, achieving complete removal of dissolved and particulate metals below ambient levels proved to be challenging. To mitigate environmental risks, this study proposes, based on the particle size analysis, the implementation of multistage filtration systems with an optimal filtration pore size for the effluent treatment. In conclusion, we highlight the potential environmental risks of IWC activities. As most metals have a strong affinity towards particles in wastewater, effective removal of particles is essential to alleviate environmental stress at IWC sites.

Effect of wastewater from the in-water cleaning of ship hulls on attached and unattached microalgae.

Environmental spills of in-water hull cleaning wastewater (HCW) containing heavy metals and biocides is inevitable, and the effects of HCW on microalgae are unknown. To investigate this, we conducted microcosm experiments by adding HCW to natural seawater. HCW samples were obtained from two different cleaning methods (soft: sponge, hard: brush), and 5 % or 10 % were added to natural seawater as treatments. Dissolved Cu concentrations were 5 to 10 times higher in the treatments than those in the control. There were significant differences in growth of unattached microalgae depending on HCW dose (chlorophyll a: 34.1 ± 0.8 µg L-1 in control vs. 12.6 ± 4.3 µg L-1 in treatments). Conversely, the biomass of attached microalgae increased with HCW dose, which was associated with most of the nutrient reduction later in the experiment, rather than unattached microalgae. Our findings suggest that HCW can significantly impact microalgal community, especially depending on spill volume.

Chemical hazard of robotic hull in-water cleaning discharge on coastal embryonic fish.

In-water cleaning (IWC) involves the removal of biofilms and foulants from the hull of a ship using brush or water jet. During IWC, several factors associated with the harmful chemical contaminants release to the marine environment, which can create "hotspots" of chemical contamination in coastal areas. To elucidate the potential toxic effects of IWC discharge, we investigated developmental toxicity in embryonic flounder, which are sensitive life stage to chemical exposure. Zinc and copper were the dominant metals, while zinc pyrithione was the most abundant biocide associated with IWC discharge in two remotely operated IWC. Discharge from IWC carried by both remotely operated vehicles (ROVs) produced developmental malformations including pericardial edema, spinal curvature, and tail-fin defects. In an analyses of differential gene expression profiles (fold-change of genes with a cutoff < 0.05) as assessed by high-throughput RNA sequencing, genes associated with muscle development were commonly and significantly changed. The gene ontology (GO) of embryos exposed to IWC discharge from ROV A activities highly enriched muscle and heart development, while cell signaling and transport were evident in embryos exposed to IWC discharge of ROV B. We analyzed the gene network by significant GO terms. In the network, TTN, MYOM1, CASP3, and CDH2 genes appeared to be key regulators of the toxic effects on muscle development. In embryos exposed to ROV B discharge, HSPG2, VEGFA, and TNF genes related to the nervous system pathway were affected. These results shed light on the potential impacts of muscle and nervous system development in non-target coastal organisms exposed to contaminants found in IWC discharge.

Comparative toxicity study of waterborne two booster biocides (CuPT and ZnPT) on embryonic flounder (Paralichthys olivaceus).

A new generation of booster biocides that include metal pyrithiones (PTs) such as copper pyrithione (CuPT) and zinc pyrithione (ZnPT) are being used as tributyltin alternatives. In the marine environment, ZnPT can easily transchelate Cu to form CuPT, and the environmental fate and persistence of these two metal pyrithiones are closely related. Although some data on the toxicity of biocides on marine fish are available, little is known about their toxicity and toxic pathway. We thus compared the toxic effects of CuPT and ZnPT on embryonic olive flounder (Paralichthys olivaceus) by investigating their adverse effects based on developmental morphogenesis and transcriptional variation. In our study, the toxic potency of CuPT was greater with respect to developmental malformation and mortality than ZnPT. Consistent with the developmental effects, the expression of genes related to tail fin malformation (including plod2, furin, and wnt3a) was higher in embryonic flounder exposed to CuPT than in those exposed to ZnPT. Genes related to muscle and nervous system development exhibited significant changes on differential gene expression profiles using RNA sequencing (cutoff value P < 0.05). Gene ontology analysis of embryos exposed to CuPT revealed affected cellular respiration and kidney development, whereas genes associated with cell development, nervous system development and heart development showed significant variation in embryonic flounder exposed to ZnPT. Overall, our study clarifies the common and unique developmental toxic effects of CuPT and ZnPT through transcriptomic analyses in embryonic flounder.

Seawater contamination associated with in-water cleaning of ship hulls and the potential risk to the marine environment.

In-water cleaning can clear-off foulants from ship hulls to prevent transportation of non-indigenous species and reduce hull friction and consequent fuel use. However, during cleaning, antifouling paint residues containing toxic substances can be released into the environment. To understand the potential risks of in-water hull cleaning, cleaning effluents were collected and analyzed for total suspended solid (TSS), particle size distribution, and metal concentrations. TSS concentrations were 97.3-249 mg/L, corresponding to release rates of 12.9-37.5 g/m2 from the hull surface. Particles with sizes of ≥8 µm contributed 75-94% of the TSS. Average Cu and Zn concentrations in the effluents were 209 µg/L and 1510 µg/L, respectively, which were used for risk assessment in two port scenarios. Although the risks vary with the scale of the hull cleaning and the ports, in-water cleaning poses clear risks to marine environments, unless the effluents are recovered or treated before being released.

Characterization of hazards and environmental risks of wastewater effluents from ship hull cleaning by hydroblasting.

Hydroblasting is used to remove biofouling and exhausted antifouling paints from ship hulls. Effluents generated from this process contain paint particles, metals, and booster biocides that may have toxic effects on organisms. To understand the potential risks of effluent discharge on marine environments, we analyzed the concentrations of metals in effluents collected during the dry-dock cleaning of ship hulls by hydroblasting. Copper and zinc were the principal metals, with concentrations ranging from 1440 to 9110 µg/L and 1800 to 22,600 µg/L, respectively. These concentrations are sufficiently high to cause harmful effects to most marine organisms. Model predictions suggested that the effluent discharge from hydroblasting posed risks to the wider marine environment of a hull-cleaning site, depending on the scale of the hull-cleaning operations and the size of the receiving environment, as well as various hydrodynamic factors. These effluents are inevitably hazardous, and their environmental release should be managed and regulated on the basis of site-specific risk assessments.

High-throughput screening of oil fingerprint using FT-IR coupled with chemometrics.

An important element of the oil spill emergency response is the ability to rapidly identify the properties of oil spilled. Chemometrics provides large numbers of multivariate analysis tools that allow for more extensive use of data. Fourier transformed infrared spectroscopy coupled with classification and prediction models such as partial least square (PLS) and PLS-DA (discriminant analysis) allows the rapid identification of oil type and characteristics. By searching for the maximum covariance with the variables of interest, PLS allows the visualization of relations between samples and variables. The framework of this study is based on two main steps: The first is classification of oil and the second is prediction of physicochemical properties. Separated into four main categories: crude, light fuel, heavy fuel, and lubricant, spectrums of 92 oils were calibrated to predict the oil type and physicochemical properties of 26 oils. The predictability and robustness of the model was further validated using weathered oil. The classification and prediction models have accuracy of >95%. Most of the PLS models have root mean square error of calibration and prediction ranging from 0.10-3.07 and 0.3-2.8, respectively. External cross validations using weathered oils showed high prediction accuracy (relative standard deviations <5%). By increasing the number of oil type and samples, this approach is a promising method and can be included as part of the oil spill fingerprinting protocols.