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Welcome to the Mariner Project "Training package for HNS Spills at sea" E-Learning page. The material was organized by CIIMAR and Action Modulers.

The material is separated in the following sections:

Introduction to Hazardous and Noxious Substances (HNS)

Copyright Cedre.jpg

The sections below address the hazardous chemicals transported by sea, the chemical spill incidents, the definition of Hazardous and Noxious Substances (HNS) and the risks associated with HNS (e.g. the behaviour of chemicals in the marine environment). A brief introduction to the advantage of classifying chemicals according to the behaviour on preparedness and response to chemical spills is also provided.


This chapter is divided into 5 sections:

  1. Hazardous chemicals transported by sea
  2. Chemical spill incidents
  3. Definition of Hazardous and Noxious Substances (HNS)
  4. Risks associated with HNS
    • Behaviour of chemicals in the marine environment
  5. Advantage of classifying chemicals according to the behaviour on preparedness and response to chemical spills


1. Hazardous chemicals transported by sea

Society is highly dependent upon chemicals for myriad applications within health care, pharmaceuticals, household goods and products, water sanitation, energy, agriculture, food preservation and transportation. Therefore, chemicals are undoubtedly essential and contribute substantially to society.




Maritime shipping is a highly efficient option for global transportation of chemicals to society. However, chemicals carried by maritime shipping (e.g. through tankers, container ships and bulk carriers) can have the potential to cause harm to human health and the environment (if spilled). These chemicals can essentially be classified into 2 categories (OPRC-HNS Protocol):

  • Oil i.e. petroleum hydrocarbons;
  • Hazardous and noxious substances (HNS) i.e. anything hazardous other than oil.


This course will focus on HNS


Source ITOPF (2014a).png


Maritime transport of HNS

The world maritime transport of HNS has grown considerably in the last few decades, including transportation to, from and within European waters, due to the continuous development of the chemical industry, the need to supply raw materials to this industry and transport high volumes of products from the industries to the customers.

Data indicate that approximately 90% of European Union external trade is transported by sea with estimates indicating:

  • up to 50,000 HNS carried by sea;
  • around 2000 HNS carried on a regular basis.

Furthermore, the International Maritime Organization (IMO)link title estimated over 200 million tonnes of chemicals traded annually by tankers.

figura


PROBLEM: The constant growth in the volume of chemicals that are transported by sea increases the RISK OF ACCIDENTAL SPILLS.

2. Chemical spill incidents Maritime chemical incidents vary in their nature and type, but typical examples include fires and explosions, leakages, spillages, and airborne releases. These incidents may be either accidental or deliberate. Additionally, incidents may occur and finish very rapidly whilst others may last for long periods. Their effects may be localised or may extent over very large areas.

It has been observed that chemical spills occur at a much lower frequency than oil spills. Therefore, the probability of shipping incidents involving HNS to occur is considered low because of the high safety standards. However, it does in fact exist as recent ship incidents involving chemicals have shown. Records from European Maritime Safety Agency (EMSA) revealed that around 100 maritime incidents involving HNS happened in European waters between 1987 and 2006. According to Cedre, ship-source HNS incidents over 10 m3 (around the world) reached the number of 126 in the period from 1998 to 2013.

FIGURA

EXAMPLES OF SHIPPING INCIDENTS INVOLVING HNS:

1988 - The tanker Anna Broere sank in the Netherlands and released 200 t of acrylonitrile (a toxic, flammable and explosive substance; giving off toxic fumes in case of fire). In this incident:  The boat had to be cut in two after lightering its cargo.  About half of the acrylonitrile cargo was recovered.  The other half had leaked out and rather quickly dispersed into the sea.

 This incident caused damage to the marine biota, but with significantly less impact than anticipated presumably because a large quantity evaporated and hence was no longer bioavailable for aquatic organisms.

2000 - The tanker Ievoli Sun sank in the English Channel and released 3998 t of styrene (a synthetic chemical considered as a marine pollutant, toxic, relatively insoluble (310 mg/L) and with a lower density than seawater (specific gravity 0.91 vs. 1.04)). After this incident:  The entire cargo of styrene was pumped out.  However, IFREMER detected styrene in the gills and the tissues of crabs in the vicinity of the wreck, since leakage was detected by a French Navy submersible drone.  Initial visual surface observation showed a slick and styrene vapours were detected at a nearby Island (Alderney).  High intensity currents resulted in significant dilution or spreading of styrene in seawater.  The possibility of chronic effects was considered to be minimal due to the behaviour of styrene following release from the vessel.

The following figure shows other cases of HNS spills (and their localisation) between 2005 and 2014:


FIGURA

Information on HNS incidents has been compiled in an online database hosted at http://www.ciimar.up.pt/hns/incidents.php. For more information on this database please consult the UNIT 4.2. Other database of spill incidents and threats in water around the world was also produced by Cedre (https://wwz.cedre.fr/en/Our-resources/Spills).

Incidents from maritime spills can potentially be devastating and can have a variety of adverse impacts. For more information on human health and/or environmental/ecological impacts resulting from chemical incidents, consult the UNIT 2.

3. Definition of Hazardous and Noxious Substances (HNS) Not all chemicals transported by sea are considered hazardous but those that are have been termed “hazardous and noxious substances” (HNS) (8 million +).

Hazardous and noxious substance (HNS) (OPRC-HNS Protocol, 2000 - definition) - any substance other than oil which, if introduced into the marine environment is likely to create hazards to human health, to harm living resources and marine life, to damage amenities or to interfere with other legitimate uses of the sea.

HOWEVER …

The HNS Convention (2010) describes HNS as a substance identified in one or more lists of the International Maritime Organization's (IMO) Conventions and Codes. Some examples of these conventions and codes can be found in table 1.

Table 1 - Examples of IMO Conventions and Codes providing HNS lists. Source: ITOPF (2014b, d). Material Conventions & Codes Bulk liquids Chapter 17 of International Code for the Construction and Equipment of Ships Carrying Dangerous Chemicals in Bulk (IBC Code) Gases Chapter 19 of International Code for the Construction and Equipment of Ships Carrying Liquefied Gases in Bulk (IGC Code) Solids in bulk Appendix 9 of Code of Safe Practice for Solid Bulk Cargoes (BC Code) if also covered by IMDG Code in packaged form Packaged goods International Maritime Dangerous Goods Code (IMDG Code)

According to table 1, the HNS (gas, liquid or solid) may be carried in bulk or as packaged goods.

The Conventions and Codes listed above are designed to ensure the safe transport of all types of chemicals.

Therefore, HNS INCLUDE (according to the HNS Convention) …

	All liquefied gases in bulk (e.g. liquefied natural gas (LNG), liquefied petroleum gas (LPG), ammonia, ethylene, propylene, ethane);
	Bulk liquids if there are potential safety, pollution or explosion hazards:

 organic chemicals (e.g. styrene, xylenes, methanol);  inorganic chemicals (e.g. acids such as sulphuric or phosphoric acids, caustic soda);  persistent and non-persistent oils of petroleum origin;

 vegetable and animal oils and fats (e.g. palm oil, soybean oil and tallow).

	Bulk solids such as fertilizers, sodium and potassium nitrates, sulphur, some types of fishmeal;
	Packaged dangerous, harmful and hazardous material.

NOT INCLUDE

	Radioactive materials;
	Most inert bulk solids (e.g. alumina, iron ore, cement, grain, etc.);
	Oil damages already covered under CLC, FUND conventions.






FINAL NOTE: The definition of an HNS as defined by the OPRC-HNS Protocol 2000 differs widely from the definition of an HNS under the International Convention on Liability and Compensation for Damage in Connection with the Carriage of Hazardous and Noxious Substances (HNS) by sea (also known as the HNS Convention).

The answer to the question "What are chemical" can also be found in the following document (pages 2-3, click in the picture):

4. Risks associated with HNS

Two factors essentially govern the hazards posed by a HNS carried at sea, namely:

	Its physical behaviour in the environment.
	Its harmful properties  (e.g. toxicity, flammability, persistence, reactivity, corrosivity, explosivity). 

Harmful properties of chemicals carried at sea can be obtained from different reference sources (e.g. GESAMP, OECD, TOXNET, WHO IPCS). These properties can have an impact on safety, environmental assets and socioeconomic activity. However, it is the physical fate of the HNS once it is released into the wider environment which determines if these properties will have an impact.


The fate of HNS material is the behaviour of the material once released into the wider environment. This is determined by the physical properties of density, volatility, and solubility of the released substance (Figure 8). Thus, these parameters determine the hazard(s) presented by the substance (toxicity, flammability, reactivity, explosivity, corrosivity, etc.).


Note: The behaviour of HNS spilled into the sea also depends on the local marine environmental conditions.

Hazardous profile of HNS According to IMO regulations, any packaged cargo transported at sea which poses a threat to people, other living organisms, property or the environment should be listed on the manifest as “Dangerous Goods” and should display the appropriate hazard labels, for example as per the International Maritime Dangerous Goods (IMDG) code or the UN Globally Harmonised System (GHS). Additionally, any packaged cargo that represents a threat to the marine environment (haz. to env. in figure 6) should also display an “Aquatic Hazard” label (Figure 6).


Figure 6 – Hazardous profile of HNS - UN Globally Harmonized System (GHS) of Classification (Source: ITOPF, 2014a).

4.1. Behaviour of chemicals in the marine environment

While most oils are immiscible with seawater and float on the sea surface, HNS chemicals are considered a threat because exhibit a wider range of behaviours once released into the environmental compartments and toxicities to marine organisms.

The Standard European Behaviour Classification (SEBC) System has been developed in order to classify chemicals according to their physicochemical behaviours when spilled into the sea. The main principle of the system is the characterization of spilled chemicals as gases (G), evaporators (E), floaters (F), dissolvers (D), sinkers (S) and the various combinations of these (GD, ED, FE, FED, FD, DE and SD) (Figures 7, 8 and 10).

Figure 7 - Diagrammatic representation of the Standard European Behaviour Classification (Source: ITOPF, 2014b).

In the Bonn Agreement Counter Pollution Manual (Chapter 26: Hazardous Material Spills), the behaviour of HNS once released was grouped as shown in Figure 8

Figure 8 - Categories of HNS behaviour and the physicochemical characteristics (density , vapour pressure and solubility ) on which the categorisation is based. The density is specified as 1023 kg/m3; this might vary in different locations depending on the salinity. Source: EMSA (2007).

As we can see in figures 7, 8 and 10 and also in table 2, the substances can have more than one physical fate in the marine environment (e.g. dissolver/evaporator, floater/dissolver). In detail, the types of physical fate (behaviour) for solids, liquids, and gas can be defined under the following groups:

	EVAPORATORS (E) - substances with a high vapour pressure (>3k Pa) and low solubility (<1%). The vapour cloud formed behaves the same way as that of a GAS (G). Such a liquid substance is also termed a “fast evaporator”.
	FLOATERS (F) - substances which do not significantly evaporate (<0.3 kPa) and dissolve (<0.1%). 

	DISSOLVERS (D) - substances which dissolve in water (>5%) and do not rapidly evaporate. The degree of solubility of the dissolvers and the turbulence in the water column will determine whether toxic concentrations in the water column will occur. 

Note: When the density of a chemical is lower than that of seawater, the parameters of vapour pressure and solubility allow to differentiate between evaporators (volatile liquids), floaters (non-volatile liquids) and dissolvers.

	SINKERS (S) - comprises all products which are denser than seawater and that are not soluble (solubility <0.1%). 
	GD - chemicals that evaporate immediately and dissolve. 
	ED - liquids which rapidly form a vapour substance (>3 kPa) and dissolve in water (>1%). Although dissolving, such substances may form flammable vapours over the water surface. 
	FE and FED - floating substances which slowly evaporate (0.3-3 kPa), but FE does not dissolve (<0.1%) and FED does (0.1-5%). For FED, the extent of solubility will determine whether toxic concentrations might occur in water. FED will completely disappear in time.

	FD - floating substances which do not significantly evaporate (<0.3 kPa) but slowly dissolve in water (0.1-5%).

	DE - substances which dissolve in water (>5%) and rapidly evaporate (>10 kPa).
	SD - substances which sink and then dissolve with a solubility >0.1%. 


The fate of HNS in the environment after a spill is illustrated in the next figure:


Source: Cedre; Removed from Liebert T (2013).


Some examples of HNS with different behaviours (when released in the environment) can be found in table 2 and figure 10.

Table 2 - Refined grouping of HNS behaviour categories once released in the marine environment. Source: HELCOM Manual on Cooperation in Response to Marine Pollution; EMSA (2007).




Figure 10 - Examples and different behaviour classes of HNS. Source: Cedre; Removed from Liebert T (2013).

Recently, GESAMP (2014) added an additional behaviour class by combining floating properties with high viscosity in order to predict longer lasting or persistent slicks. These substances (e.g. Decanoic acid, 1-dodecanol, nonylphenol) are rated as ‘Fp’ (persistent floater). More information on behaviour of chemicals in the marine environment can be found in the following documents:

5. Advantage of classifying chemicals according to the behaviour on preparedness and response to chemical spills There is growing international awareness of the need for safe and effective contingency arrangements for responding to chemical spills.

However, HNS preparedness and response is less well defined (and not as straightforward) than that for oil spills due to the great complexity and variety of chemicals transported by sea (their behaviour once spilt, different properties, hazards such as toxicity, etc.). Furthermore, it is known that the consequence of a chemical spill can be more wide reaching than that of oil.

Classifying the chemicals, whether gases, liquids or solids, according to the behaviour exhibited when released into the marine environment, is a useful tool when developing a response strategy. This leads to a need for a relatively low number of generally applicable response options in a spill event. Additionally, based on information on the short-term behaviour of the spilled compound, it is possible to define a detection and monitoring plan well adapted to the geographical location, particular sea and atmospheric conditions, hydrodynamics, and characteristics of the water column and sea bottom compartments. Therefore, it is important to understand the behaviour of HNS spilled in order to decide the most effective response method and also recognise the health and safety implications.


References

Bonn Agreement (2017). Bonn agreement counter pollution manual. Available at: http://www.bonnagreement.org/manuals (accessed March 30, 2017).

Cedre (2009). Review of chemical spills at sea and lessons learnt. INTERSPILL 2009 Conference White Paper Technical Appendix. Marseille, France (40 pp.).

Cunha I, Neuparth T, Moreira S, Santos MM, Reis-Henriques MA (2014). Management of contaminated marine marketable resources after oil and HNS spills in Europe. Journal of Environmental Management 135: 36-44.

Cunha I, Moreira S, Santos MM (2015). Review on hazardous and noxious substances (HNS) involved in marine spill incidents - an online database. Journal of Hazardous Materials 285: 509–516.

Cunha I, Oliveira H, Neuparth T, Torres T, Santos M (2016). Fate, behaviour and weathering of priority HNS in the marine environment: an online tool. Marine Pollution Bulletin 111 (1-2): 330-8.

EMSA (2007). European Maritime Safety Agency. Action Plan for HNS Pollution Preparedness and Response. Available at: http://www.emsa.europa.eu/hns-pollution/123-hns-pollution/260-action-plan-for-hns-pollution-preparedness-and-response.html (accessed March 16, 2017).

GESAMP (IMO/FAO/UNESCO-IOC/WMO/WHO/IAEA/UN/UNEP Joint Group of Experts on the Scientific Aspects of Marine Environmental Protection) (2014). Revised GESAMP Hazard Evaluation Procedure for Chemical Substances Carried by Ships, 2nd edition. Rep. Stud. GESAMP No. 64, 126 pp.

HASREP (2005). Response to harmful substances spilt at sea. Prepared by the Alliance of Maritime Regional Influences in Europe (AMRIE) Centre de Documentation, de Recherche et d'Expérimentations Sur Les Pollutions Accidentelles Des Eaux. (CEDRE) and TNO Built Environment and Geosciences, The Netherlands (38 pp.).

IMO (International Maritime Organisation) (2000). Protocol on Preparedness, Response and Co-operation to Pollution Incidents by Hazardous and Noxious Substances (OPRC-HNS Protocol). Available at: http://www.imo.org/en/About/Conventions/ListOfConventions/Pages/Protocol-on-Preparedness,-Response-and-Co-operation-to-pollution-Incidents-by-Hazardous-and-Noxious-Substances-(OPRC-HNS-Pr.aspx (accessed March 9, 2017).

IMO/UNEP (2003). Regional Information System, Part D, Operational Guides and Technical Documents, Section 11, Practical Guide to Marine Chemical Spills, REMPEC (Regional Marine Pollution Emergency Response Centre for the Mediterranean Sea).

International Oil Pollution Compensation FUND 1992 (2005). Guide to the implementation of the HNS Convention. 27 pp.

ITOPF (2014a). Session 1 - Overview of Hazardous and Noxious Substances. Available at: http://www.hnsconvention.org/fileadmin/IOPC_Upload/hns/files/1%20Overview%20of%20HNS-Risk%20and%20Incidents%202014_ITOPF.pdf (accessed March 21, 2017)

ITOPF (2014b). Response to marine chemical incidents. Technical Information paper n.º 17. Available at: file:///D:/Desktop/TIP17ResponsetoMarineChemicalIncidents%20(2).pdf (accessed February 15, 2017).

ITOPF (2014c). Chemical Fate and Effects. Available at: http://www.itopf.com/knowledge-resources/documents-guides/hazardous-and-noxious-substances-hns/chemical-fate-and-effects/ (accessed March 3, 2017).

ITOPF (2014d). Hazardous and Noxious Substances (HNS). Available at: http://www.itopf.com/knowledge-resources/documents-guides/hazardous-and-noxious-substances-hns/ (accessed February 14, 2017).

Liebert T (2013). Claims procedures for HNS: How they might work. Available at: http://www.hnsconvention.org/fileadmin/IOPC_Upload/hns/files/Claims.pdf (accessed February 23, 2017)

MARINER (2016). Mariner project. Available at: http://mariner-project.eu/about#objectives (accessed March 23, 2017)

Neuparth, T, Moreira S, Santos MM, Reis-Henriques MA (2011). Hazardous and noxious substances (HNS) in the marine environment: prioritizing HNS that pose major risk in a European context. Marine Pollution Bulletin 62: 21–28.

Neuparth T, Capela R, Rey-Salgueiro L, Moreira SM, Santos MM, Reis-Henriques MA (2013). Simulation of a hazardous and noxious substances (HNS) spill in the marine environment: lethal and sublethal effects of acrylonitrile to the European seabass. Chemosphere 93: 978–985.

Solé M, Lima D, Reis-Henriques MA, Santos MM (2008a). Stress biomarkers in juvenile Senegal sole, Solea senegalensis, exposed to the water-accommodated fraction of the “prestige” fuel oil. Bulletin of Environmental Contamination and Toxicology 80: 19–23.

Solé M, Lobera G, Lima D, Reis-Henriques MA, Santos MM (2008b). Esterases activities and lipid peroxidation levels in muscle tissue of the shanny Lipophrys pholis along several sites from the Portuguese coast. Marine Pollution Bulletin 56: 999–1007.

Environmental Impacts

Ecology and Publich Health

The sections below describe the impacts (environmental/ecological, public health and socioeconomic impacts) of HNS spills at sea.

This chapter is divided into five sections:

1. Introduction

2. Environmental / Ecological impacts

3. Public health impacts

4. Environmental and public health impacts of the main HNS behaviour groups

5. Socioeconomic impacts

6. Important documents


FIGURA


1. Introduction

Considering our society's dependence on chemicals and consequently the constant growth in the volume of chemicals that are transported by sea, it is essential to understand their potential hazardous impacts in case of a spill.

Incidents of HNS can encompass a wide range of temporal and spatial impacts, varying from short-term localised events to incidents covering vast areas and lasting for many months. The adverse impacts of chemical incidents can include human health effects, environmental and ecological damage, and commercial and amenity disruption.

2. Environmental / Ecological impacts

Shipping incidents of HNS can cause immediate and potential long-term adverse effects on marine habitats and ecosystems (e.g. destruction of marine habitats; sub-lethal and lethal effects on marine organisms; visible detriment to beaches, coastlines and wildlife).


FIGURA


Ecosystems may take many years to recover from an incident, particularly when the chemicals involved are persistent, of low solubility and low volatility.

The effects of an HNS released into the marine environment will depend on a number of FACTORS such as:

  • Behaviour of the substance.
  • Toxicity of the material .
  • Quantities involved.
  • Resulting concentrations in the water column and/or sea floor.
  • Sea conditions in the affected zone such as turbulence, surface and deep currents, presence of thermoclines and haloclines (i.e. local oceanography). They affect the chemical distribution through the water column and/or its loss at the water surface.
  • Length of time organisms are exposed to that concentration (i.e. exposure time).
  • Level of tolerance of the organisms (which varies greatly among different species and during their life cycles).


EFFECTS…

Incidents involving releases to marine waters have the benefit of sea and air dilution, to decrease the concentration of a substance to below a lethal dose. However, lower doses can produce SUBLETHAL EFFECTS to marine organisms over a wider area. These effects can produce some form of damage which may be detrimental to marine environment (i.e. individual organisms, species, populations or marine communities) over a longer term, depending upon the persistence of the released HNS in the marine environment. For example, chemically-induced stress can reduce the overall ability of an organism to grow, reproduce, feed (i.e. to survive) or otherwise function normally within a few generations. More specifically, sublethal effects include:

  • Damage to internal organs;
  • Damage to fins;
  • Pre-cancerous growths;
  • Skeletal deformities;
  • Reduction in reproductive success.


These effects may not be readily detectible in individuals but could cause changes in the community structure of a marine area impacted by an HNS incident.

Some forms of HNS material (where not directly toxic) can damage the marine ecosystems by causing CHANGES IN THE ENVIRONMENT. Such changes include:

  • Variation in salinity and pH, together with deoxygenation when material is broken down or used biologically in the marine environment (e.g. fertilisers, palm oil, etc.).

Changes in environmental conditions can induce LETHAL EFFECTS in marine ecosystems. However, it should be noted that:

  1. Such effects can be limited to the wreck site and immediate dilution area.
  2. The significance of such effects is dependent on the location of the incident (e.g. changes in salinity and oxygen content in an estuarine or already polluted area may have little impact due to the natural tolerance of the resident marine community, while there may be a greater effect on pristine reef communities).

Biologically inert material which does not have a toxic or environmental effect may have an impact due to SMOTHERING OR BY CHANGING THE PHYSICAL NATURE OF AN AREA (e.g. a sinker settling over a bottom, resulting in a change to the habitat of the benthic ecosystem). This is also likely to be limited to the immediate area of the incident site, although currents can redistribute HNS material. In addition to HNS behaviour, processes such as BIOACCUMULATION (accumulation of the substances within organisms themselves, resulting in detrimental impacts over a much wider area, even to a global scale) and BIOMAGNIFICATION determine the compartments of the food web affected. The characteristics of some HNS (particularly heavy metals and some organic compounds) can result in bioaccumulation. Sessile marine species that filter seawater for food, such as bivalve molluscs, are particularly vulnerable to this phenomenon. Subsequent biomagnification may also occur if the chemicals can be passed on, following the food chain up to higher predators (e.g. top predators of marine communities - fish, birds, marine mammals and humans).

Current knowledge of HNS effects … An understanding of the ecological hazards involved in HNS spills is less well recognized than that involving oil spills. There is a current paucity of knowledge about the effects of HNS on marine biota and the relatively few data available on the HNS ecotoxicology are mostly from experiments conducted with freshwater organisms. For example, reproduction impairment due aniline toxicity has been reported for freshwater Crustacea Daphnia magna (Abe et al., 2001; Kühn et al., 1989) and acute toxicity shown for sand shrimp Crangon septemspinosa (McLeese et al., 1979).

Therefore, the toxicity and ecological impacts of HNS on marine organisms are poorly understood, making it difficult to predict the effects on marine ecosystems and to prepare contingency plans for these substances.

In order to respond to incidents involving HNS, the systematic classification of scientific ecotoxicological data for marine organisms should be a priority issue.

Therefore, some recent studies (see below) were performed to improve the knowledge on the effects of HNS to marine organisms:

FIGURA


3. Public health impacts

Environmental impacts are often more obvious than human health effects. However, human health effects caused by HNS incidents can include:

      Toxicological effects (acute  and chronic ) - such effects may happen when humans are exposed to chemicals after a chemical spill. The main routes of exposure are through:
  • Inhalation (gaseous or volatile chemicals; e.g. products of combustion or an airborne plume);
  • Ingestion (contamination of water supplies or food (e.g. fish));
  • Dermal contact (release of solids or liquids).

According to the revised GESAMP hazard evaluation procedure, the principal mode of human exposure after spillage is expected to be through vapours. Thus, the human exposure is likely to occur predominantly from air-borne contamination and consequently inhalation exposure.

Both acute and chronic health effects are recognized following acute releases of chemicals. These effects may affect all major body systems (e.g. cardiovascular, respiratory, immunological and neurological systems). Reproductive effects may occur whilst some chemicals may be teratogenic (i.e. cause birth defects). Some chemicals may also be associated with cancer (i.e. carcinogens). Moreover, some chemicals may have a secondary impact upon those coming into contact with casualties (e.g. health workers) and may also have delayed effects such as respiratory oedema.

Some examples of pathologies due to chronic intoxication can be seen in the next picture:

Source: Cedre


	Mental health effects - Such effects are determined by exposure to the chemicals spilled and the event itself, even if exposure is unlikely. Major chemical incidents have the potential to disrupt the lives of victims through impacting upon health, loss of relatives or other lives, property and employment as well as through environmental degradation. Victims of incidents can experience long-lasting mental health problems.
	Physical effects - for example, explosions following heating of tanks containing chemicals can result in traumatic injuries from shock waves, projectiles and fragments. Additionally, fires can produce physical injury through the production of heat.

Prioritisation of HNS

A methodology has been established for prioritisation of HNS, based upon potential public health risks. HNS were assessed using conventional methodology based upon acute toxicity, behaviour and reactivity. Analysis of 350 individual HNS identified the highest priority HNS as being those that present an inhalation risk. For more information consult Harold and collaborators (2014).

4. Environmental and public health impacts of the main HNS behaviour groups

Substances released into the marine environment could pass into the air (gas clouds), onto the water surface (floaters), into the water column (dissolvers), to the sea floor (sinkers), or a combination of these. These substances may contaminate indirectly, all the organisms in these compartments and other users of these compartments in the event of an accident at sea. Specific information on the HNS behaviour (main groups) in the environment, their environmental and public health impacts as well as the organisms / species most affected can be found HERE.

Therefore, substances with different behaviours at sea provide different impacts to marine organisms. However, DISSOLVERS AND SINKERS are the substances that might cause the HIGHEST POTENTIAL ECOLOGICAL IMPACTS ON THE MARINE ENVIRONMENT after a spill as they will disperse easily, and hence may be bioavailable for aquatic organisms, both in the water column and the sediments.

From the HUMAN HEALTH PERSPECTIVE, the chemicals of priority concern are those that have some CAPACITY FOR EVAPORATION (i.e. gases and evaporators; e.g. toluene, benzene) and which may induce a health effect. These substances would tend to be governed by atmospheric parameters.

Hazards to marine environment and humans Human populations as well as the marine environment can be exposed to spilled hazardous chemical substances, as already mentioned. Nine potential hazards can be distinguished when chemical substances enter the marine environment. The hazards are listed in Table 1 and described accordingly for each behaviour category.

Table 1 - Most relevant hazards of chemical substances within a behaviour category for humans and the marine environment.


FIGURA

Therefore, each behaviour has its own relevant hazard aspects. For example, toxicity to human populations and explosivity are typical hazard aspects of substances which pass into the air after a release as can be observed in table 1.


5. Socioeconomic impacts

Some examples of socioeconomic impacts due to an HNS spill are:

	Commercial value of marine resources reduced. This can be observed, for example, in:
  • Marketed fish with fin erosion, skeletal and/or growth deformities;
  • Seafood that present a change in the organoleptic characteristics (a phenomenon known as Tainting).
	Closure of fishing and aquaculture areas due to a contamination of commercial fish and shellfish by a toxic substance that have the capacity to bioaccumulate. The loss of fishing and aquaculture resources implies economic losses from business interruption.
	Amenity value of an area reduced for economic drivers such as tourism because of the contamination of this area (e.g. through the pollution of amenity beaches and bathing/recreation waters).

There is also the impact of “public perception”, whereby the impact of an incident can be magnified if public opinion considers that the area is not safe to visit or consumer products (e.g. fish, shellfish, etc.) from the location are polluted. Some examples of property damage / economic losses can be seen in the following figure:


FIGURA

6. IMPORTANT DOCUMENTS

The International Maritime Organization created a group of experts on Scientific Aspects of Marine Environmental Protection (GESAMP). Extensive work has been undertaken by this group for the international conventions to identify the hazards associated with HNS material and classify the potential safety, health and environmental risks. GESAMP, an advisory body to the United Nations, has published evaluations of the effects of substances transported by ships on the marine environment (hazard evaluation procedure - 1st edition: 2002). This easily accessible and simple guide can provide an important first step in evaluating the severity of a chemical spill. The properties of the chemicals have been evaluated in relation to a number of predefined effects:

A = Bioaccumulation and biodegradation B = Aquatic toxicity (acute and chronic aquatic toxicity) C = Acute mammalian toxicity D = Irritation, corrosion and long term mammalian health effects E = Interference with other uses of the sea

The 2nd edition of the hazard evaluation procedure of GESAMP was published recently:

  FIGURA


Data regarding effects of individual HNS cargoes can also be obtained from substance specific Safety Data Sheets (SDS) which summarise the various hazards associated with each substance. SDS commonly provides toxicological and ecological information, etc.

References

Abe T, Saito H, Niikura Y, Shigeoka T, Nakano Y (2001). Embryonic development assay with Daphnia magna: application to toxicity of aniline derivatives. Chemosphere 45: 487–495.

Alcaro L, Amato E, Cabioch F, Farchi C, Gouriou V, Wrubl C (2007). DEEPP project, development of European guidelines for potentially polluting shipwrecks. ICRAM, Istituto Centrale per la Ricerca Scientifica e Tecnologica Applicata Al Mare. CEDRE, Centre de Documentation de recherché et d'expérimentations Sur Les Pollutions Accidentelles Des Eaux (163 pp.).

Bonn Agreement (2017). Bonn agreement counter pollution manual. Available at: http://www.bonnagreement.org/manuals (accessed March 31, 2017).

Cunha I, Neuparth T, Moreira S, Santos MM, Reis-Henriques MA (2014). Management of contaminated marine marketable resources after oil and HNS spills in Europe. Journal of Environmental Management 135: 36-44.

Cunha I, Moreira S, Santos MM (2015). Review on hazardous and noxious substances (HNS) involved in marine spill incidents - an online database. Journal of Hazardous Materials 285: 509–516.

EMSA (2007). European Maritime Safety Agency. Action Plan for HNS Pollution Preparedness and Response. Available at: http://www.emsa.europa.eu/hns-pollution/123-hns-pollution/260-action-plan-for-hns-pollution-preparedness-and-response.html (accessed March 16, 2017).

GESAMP (IMO/FAO/UNESCO-IOC/WMO/WHO/IAEA/UN/UNEP Joint Group of Experts on the Scientific Aspects of Marine Environmental Protection) (2002). The Revised GESAMP Hazard Evaluation Procedure for Chemical Substances Carried by Ships. GESAMP Reports and Studies No. 64. London (137 pp.).

GESAMP (IMO/FAO/UNESCO-IOC/WMO/WHO/IAEA/UN/UNEP Joint Group of Experts on the Scientific Aspects of Marine Environmental Protection) (2014). Revised GESAMP Hazard Evaluation Procedure for Chemical Substances Carried by Ships, 2nd edition. GESAMP Reports and Studies No. 64. London (126 pp.).

Harold P, Russell D, Louchart P (2011). Risk prioritisation methodology for hazardous & noxious substances for public health. Arcopol Report (The Atlantic Regions' Coastal Pollution Response). Available at:

http://arcopol.eu/index.php?/=/section/resources/sub/r_hns/pag/4/resource/12 (accessed 31 March 2017)).

Harold PD, Souza AS, Louchart P, Russell D, Brunt H (2014). Development of a risk based prioritisation methodology to inform public health emergency planning and preparedness in case of accidental spill at sea of hazardous and noxious substances (HNS). Environment International 72, 157–163.

Hodgson E (2010). A textbook of modern toxicology. 4th edition. John Wiley & Sons, Inc., Hoboken, New Jersey. 648 pp.

ITOPF (2014a). Chemical Fate and Effects. Available at: http://www.itopf.com/knowledge-resources/documents-guides/hazardous-and-noxious-substances-hns/chemical-fate-and-effects/ (accessed March 3, 2017).

ITOPF (2014b). Chemical Spill Response Strategies. Available at: http://www.itopf.com/knowledge-resources/documents-guides/hazardous-and-noxious-substances-hns/chemical-spill-response-strategies/ (accessed March 3, 2017)

Kühn R, Pattard M, Pernak KD, Winter A (1989). Results of the harmful effects of water pollutants to Daphnia magna in the 21 day reproduction test. Water Research 23: 501–510.

Liebert T (2013). Claims procedures for HNS: How they might work. Available at: http://www.hnsconvention.org/fileadmin/IOPC_Upload/hns/files/Claims.pdf (accessed February 23, 2017)

Mamaca E, Bechmann RK, Torgrimsen S, Endre Aas E, Bjørnstad A, Baussant T, Le Floch S (2005). The neutral red lysosomal retention assay and Comet assay on haemolymph cells from mussels (Mytilus edulis) and fish (Symphodus melops) exposed to styrene. Aquatic Toxicology 75: 191-201.

McGowan T, Sheahan D, Cunha I, Oliveira H, Santos M (2013). Determination of acute and chronic toxicity of priority HNS upon representatives of different marine plant and animal taxa. ARCOPOLplus report (Improving maritime safety and Atlantic Regions’ coastal pollution response through technology transfer, training and innovation). Available at: http://www.arcopol.eu/?/=/section/resources/sub/r_hns/pag/1/resource/83 (accessed 4 April 2017).

McLeese D, Zitko V, Peterson M (1979). Structure-lethality relationships for phenols, anilines and other aromatic compounds in shrimp and clams. Chemosphere 8: 53–57.

Neuparth, T, Moreira S, Santos MM, Reis-Henriques MA (2011). Hazardous and noxious substances (HNS) in the marine environment: prioritizing HNS that pose major risk in a European context. Marine Pollution Bulletin 62: 21-28.

Neuparth T, Moreira SM, Santos MM, Reis-Henriques MA (2012). Review of oil and HNS accidental spills in Europe: identifying major environmental monitoring gaps and drawing priorities. Marine Pollution Bulletin 64: 1085-1095.

NOAA (2015). NOAA'S Response and Restoration Blog. Available at: https://usresponserestoration.wordpress.com/tag/chemical-spills/ (accessed March 3, 2017)

Purnell K (2009). Are HNS Spills more dangerous than oil spills? Conference Proceedings, Interspill, Marseille, 12-14 May 2009.

Environmental Monitoring

Monitoring (e.g. Monitoring Protocols). Unit 3 – Environmental monitoring


The sections below address the post-incident monitoring for environmental impact assessment (e.g. explain why is necessary an effective and pre-considered post-incident monitoring). The sampling strategies as well as the main scientific approaches employed in monitoring programmes in the case of an accidental HNS marine pollution event are described. Furthermore, a recommended baseline battery of biomarkers and bioassays for use in post-incident monitoring and the relevance of indicator /sentinel species are also provided. The last topic of this unit describes the major gaps and environmental monitoring priorities (e.g. standardized guidelines).

To complement this chapter see the following video interview on environmental post-spill monitoring:

LINK Documento pdf?

This chapter is divided into 4 sections:

1. Post-incident monitoring for environmental impact assessment 2. Sampling strategies 3. Main scientific approaches employed 3.1. Ecotoxicology in post-spill monitoring 4. Major gaps and environmental monitoring priorities


FIGURA


1. Post-incident monitoring for environmental impact assessment

A fully integrated and effective response to a chemical spill at sea must include a well planned and executed post-incident assessment of environmental contamination and damage.


Environmental post-incident monitoring is a set of integrated data-collecting activities to characterise and monitor the quality of a defined environment after an incident such as an HNS spill. Monitoring data may be used to compare spatial or temporal trends in relevant parameters as required for the preparation of an environmental impact assessment.


“Why is effective and pre-considered post-incident monitoring necessary?”

Six key reasons to respond to this question are proposed in the following paper:


Impact assessment is a process through which the consequences of an event (such as a marine HNS spill) or process are evaluated through the monitoring of key parameters and compared to a previous or “normal” status. Impact assessment aims to establish the magnitude, type, and significance of any monitored changes and for them to be “quantified” as far as possible.


Therefore, after chemical spill incidents …

Post-spill monitoring and impact assessment studies may be required to investigate and understand the behaviour and fate of a chemical spill, its effects and any associated clean-up response which, in turn, helps to address any wider concerns (e.g. from the public).

The arrangement and co-ordination of post-incident monitoring and impact assessment need to consider sampling design, biological effects, chemical analysis and collection/interpretation of expert local knowledge, etc.


2. Sampling strategies

Sampling should include both impacted and reference (unimpacted) sites, ideally with similar characteristics. Sites that are not impacted at the time of sampling but are likely to be impacted later or during the incident (e.g. as indicated by predictive modelling of the trajectory of the spilled material) can provide excellent reference (pre-incident) information. The range of samples to be collected can be very wide, including:

	Water;
	Subtidal and intertidal sediments;
	Subtidal and intertidal biota;
	Coastal (supratidal) biota and sediments;
	Commercial fish and shellfish; 
	Birds;
	Samples of the spilled chemical(s) from the sea surface or from beaches. Dissolved concentrations of contaminants are usually very low even during marine incidents.

Samples should be taken in a representative manner and in accordance with guidelines, protocols and operating procedures established during the planning and preparedness phase.


FIGURA

3. Main scientific approaches employed In the case of an accidental HNS marine pollution event a monitoring programme is usually set up applying three types of scientific approaches:


	Monitoring of chemical contamination (i.e. measurement of the chemical concentration (through chemical analysis) in the various marine compartments (water, air, sediments, organisms tissues).

FIGURA

	Monitoring of biological responses at sub-individual and individual level (e.g. physiological and epidemiological markers; biomarkers of exposure/effect (e.g. enzyme levels); biological responses in ecotoxicological assays).

FIGURA

	Ecological monitoring at population and/or community level (population dynamic and/or community structure parameters e.g. abundance, mortality, etc.) (Ecological domains: Marine mammals; Birds; Fish/Shellfish; Plankton; Benthos);

For example, in case of a spill with evaporators or gases, it is essential to:

	Evaluate the presence and concentration of contaminants in air (monitoring the plume).
	Monitor oxygen levels, flammability and toxic levels.

FIGURA


An overview of main scientific monitoring approaches and methodologies can be found in the following articles:



FIGURA


3.1. Ecotoxicology in post-spill monitoring

Ecotoxicological methods can be used as powerful tools in post-incident monitoring and the assessment of actual or potential impacts.

It is highly recommended that a baseline standard approach is available, including standardised techniques, to facilitate the prompt deployment of testing following a spill incident. Tables 1 and 2 outline a recommended baseline approach.


Table 1 - Recommended baseline battery of bioassays for use in post-incident monitoring.


TABELA


Table 2 - Recommended baseline battery of biomarkers for use in post-incident monitoring (short-term).

TABELA


Biomarkers Biomarkers do not directly provide information concerning impacts on the higher levels of biological organization (e.g. population, community, and ecosystem) considered in ecotoxicology. Nevertheless, biomarkers often provide important tools for discerning contaminant exposures and potential impacts of ecological relevance, as well as sensitive early warning signals or incipient ecological damage. Hence, biomarkers play an important role in monitoring studies in the evaluation of the effectiveness of remedial action of xenobiotic effects, to assess the quality of the environment and how it changes over time.

Possible biomarkers suitable for ecotoxicological assessment and monitoring in both estuarine and marine systems can be found in the following article:

 The term biomarker has been generally used to refer to a xenobiotically induced variation in cellular, or biochemical components as well as processes, structures, or functions that are measurable in a biological system or samples, resulting in an observable change (not necessarily pathological) in a normal status. This definition includes biochemical, physiological, histological, morphological, and behavioural measures. In other words, a biomarker can be defined as a biochemical, genetic, or molecular indicator that can be used to screen disease or toxicity. Therefore, this parameter can be used as an indicator of exposure, effect, or susceptibility and may be a metabolite, enzyme, or cell surface marker, among others.


 Xenobiotic: (1) A general term used to describe any chemical interacting with an organism that does not occur in the normal metabolic pathways of that organism. The use of this term in lieu of “foreign compound” among others, has gained wide acceptance. (2) A substance not normally present in the environment, such as a pesticide or pollutant

Indicator / Sentinel species An indicator species is any biological species whose presence, absence or abundance reflects a specific environmental condition, such as pollution, species competition or climate change. Species that react positively to environmental contamination or whose behaviour suffers a modification compared to a normal status can also be considered indicator species. Hence, indicator species can be among the most sensitive species in an ecosystem and sometimes act as an early warning in biomonitoring studies (e.g. sentinel species).

Where a particular habitat is at threat or is already impacted, it is recommended the use of sentinel species (coastal organisms such as shanny fishes (Lipophrys pholis), mussels (Mytilus galloprovincialis, etc.)) that are representative of that particular environment (e.g. species that play an important role in the maintenance of the ecosystem sustainability) in impact assessment and recovery. As part of environmental monitoring programmes, marine researchers carry out analyses in sentinel species from different locations and in different seasons. These species may give the first signal of environmental contamination and are essential to monitor the efficiency of cleaning and environmental restoration activities.

FIGURA

Note: The ultimate selection of target species and assays (bioassays/biomarkers) will require a case-by-case approach, depending on the ecosystem affected (e.g. offshore, coastal or estuarine) and the financial constraints of the monitoring program.

4. Major gaps and environmental monitoring priorities

The major gaps and environmental monitoring priorities that have been mentioned in the literature are as follows:

	Lack of research coordination - Priority to multidisciplinary studies rather than to particular scientific interests.
	Lack of reference/baseline data - Priority to set up reference databases by performing long-term monitoring programmes.
	Lack of knowledge on the biology of the selected species - Priority to use well validated and ecological relevant indicator species.
	Lack of information related with the hazards and consequences of HNS spills - Priority to gather information on the ecological hazards of HNS and to set up monitoring studies following major HNS spills.

Note: Toxicity bioassays with different species (e.g. sea urchin (Paracentrotus lividus), amphipod (Gammarus locusta), turbot (Scophthalmus maximus)) have been performed in the last years by CIIMAR in order to increase the information related with the hazards and consequences of HNS spills.


FIGURA


	Lack of knowledge on long-term effects of the spills - Priority to set long-term monitoring programmes and funding allocation.
	Standardisation of procedures and guidelines for conducting monitoring programmes following a spill.

These major gaps and environmental monitoring priorities are explained in more detail in Neuparth et al. (2012).

Relevance of Guidelines and protocols

Every accidental spill is unique and therefore any monitoring programme will need to have some elements adapted to the local circumstances in order to consider all lines of evidence and specificities of the incident. Nonetheless, although monitoring programmes should be flexible, the establishment of guidelines and standard procedures (protocols) for conducting monitoring programmes would be of great benefit, as mentioned before.

Guidelines would provide benefits in developing a framework for best approach for a range of essential post-incident monitoring activities including:

	Monitoring programme development; 
	Survey design;
	Collection, transport and storage of samples (water, sediments and biota), for which biological and chemical analysis techniques are available and their purposes, ecological and ecotoxicological assessment techniques, statistical treatment of data and presentation of the outputs are in the most appropriate ways for the intended audience.

Therefore, the implementation of guidelines and protocols are essential to strengthen monitoring programmes in terms of speed, identification of the expertise needed (e.g. modellers, ecotoxicologists, marine ecologists), cost effectiveness, use of the best practices and improve integration and coordination.

FIGURA

Some guidelines and protocols on environmental monitoring (e.g. Post-incident monitoring guidelines developed under the PREMIUM project) can be found in the Hazardous and Noxious Substances Online Platform (explained in unit 4.2). To access these documents click HERE.


FIGURA


References Aphotomarine (2014). Aphotomarine. Mytilus galloprovincialis. Available at: http://www.aphotomarine.com/bivalve_mytilus_galloprovincialis_galician_mussel.html (accessed May 1, 2017)

Bocquené G, Galgani F (1998). Biological effects of contaminants: Cholinesterase inhibition by organophosphate and carbamate compounds. ICES Techniques in Marine Environmental Sciences no. 22. 12p.

Castro M, Santos MM, Monteiro NM, Vieira N (2004). Measuring lysosomal stability as an effective tool for marine coastal environmental monitoring. Marine Environmental Research 58: 741-745.

Hodgson E (2010). A textbook of modern toxicology. 4th edition. John Wiley & Sons, Inc., Hoboken, New Jersey. 648p.

ISO (1999). ISO 14669:1999(E) Water quality: determination of acute lethal toxicity to marine copepods (Copepoda, Crustacea). International Organization for Standardization, Geneva, Switzerland.

ISO (2006). ISO 14442:2006(E) Water quality: guidelines for algal growth inhibition tests with poorly soluble materials, volatile compounds, metals and waste water. International Organization for Standardization, Geneva, Switzerland.

ITOPF (2014). Session 1 - Overview of Hazardous and Noxious Substances. Available at: http://www.hnsconvention.org/fileadmin/IOPC_Upload/hns/files/1%20Overview%20of%20HNS-Risk%20and%20Incidents%202014_ITOPF.pdf (accessed March 21, 2017)

Kirby MF, Law RJ (2010). Accidental spills at sea – Risk, impact, mitigation and the need for co-ordinated post-incident monitoring. Marine Pollution Bulletin 60: 797–803.

Klaassen CD (2008). Casarett and Doull’s Toxicology. The Basic Science of Poisons. 8th edition. McGraw-Hill Education, LLC, New York, USA. 1454p.

Krüger (1795-1797). Lipophrys pholis. Wikispecies. Available at: https://species.wikimedia.org/wiki/Lipophrys_pholis (accessed May 1, 2017)

Law RJ, Kirby MF, Moore J, Barry J, Sapp M, Balaam J (2011). PREMIAM - Pollution Response in Emergencies Marine Impact Assessment and Monitoring: Post-incident monitoring guidelines. Science Series Technical Report. Cefas, Lowestoft, 146: 164p.

Moore MN, Lowe D (2004). Biological effects of contaminants: Measurement of Lysosomal membrane stability. ICES Techniques in Marine Environmental Sciences no. 36. 31p.

Neuparth T, Moreira SM, Santos MM, Reis-Henriques MA (2012). Review of oil and HNS accidental spills in Europe: identifying major environmental monitoring gaps and drawing priorities. Marine Pollution Bulletin 64: 1085-1095.

OECD (2013). OECD Guidelines for the Testing of Chemicals, Section 2: Effect on Biotic Systems. Test No. 236: Fish Embryo Acute Toxicity (FET) Test. OECD. 22p.

Radović JR, Rial D, Lyons BP, Harman C, Viñas L, Beiras R, Readman JW, Thomas KV, Bayona JM (2012). Post-incident monitoring to evaluate environmental damage from shipping incidents: Chemical and biological assessments. Journal of Environmental Management 109: 136-153.

Robinson L, Thorn I (2005). Toxicology and ecotoxicology in chemical safety assessment. Blackwell Publishing Ltd., Oxford, UK. 157p.

Thain JE (1991). Biological effects of contaminants: oyster (Crassostrea gigas) embryo bioassay. ICES Techniques in Marine Environmental Sciences no. 11. 12p.

Thain J, Bifield S (2001). Biological effects of contaminants: Sediment bioassay using the polychaete Arenicola marina. ICES Techniques in Marine Environmental Sciences no. 29. 16p.

Thain J, Roddie B (2001). Biological effects of contaminants: Corophium sp. sediment bioassay and toxicity test. ICES Techniques in Marine Environmental Sciences no. 28. 21p.

Van der Oost R, Beyer J, Vermeulen NPE (2003). Fish bioaccumulation and biomarkers in environmental risk assessment: a review. Environmental Toxicology and Pharmacology 13(2): 57-149.

Widdows J, Staff F (2006). Biological effects of contaminants: Measurement of scope for growth in mussels. ICES Techniques in Marine Environmental Sciences no. 40. 30p.

Advanced Tools for Preparedness & Response

In the next sections are presented several multidisciplinary approaches to hns spill preparedness and response.

Situational Awareness And Common Operating Picture

The Mariner Platform is a web GIS that integrate multiple information layers and efficiently manage the response to an eventual spill. It provides operational meteorological, hydrodynamics and waves modelling and online on-demand hns ecotoxicology spill.

Integration of Online Databases in Preparedness & Response

Previous HNS Incidents and HNS Products Unit 4.2 – Integration of online databases in preparedness & response

The sections below address the Hazardous and Noxious Substances Online Platform and two online databases (e.g. how to use them; their importance) elaborated by the Interdisciplinary Centre of Marine and Environmental Research (CIIMAR) of the University of Porto (Portugal): a) Hazardous and Noxious Substances Spill Incidents; b) Fate, weathering, behaviour and toxicity of priority Hazardous and Noxious Substances.

This chapter is divided into 4 sections:

1. Hazardous and Noxious Substances Online Platform 2. Hazardous and Noxious Substances Spill Incidents - an online database 3. Fate, weathering, behaviour and toxicity of priority Hazardous and Noxious Substances - an online tool 4. Relevance of the online databases

1. Hazardous and Noxious Substances Online Platform

The Hazardous and Noxious Substances Online Platform was elaborated by CIIMAR in the framework of the ARCOPOL Platform project (Platform for improving maritime coastal pollution preparedness and response in Atlantic regions) and can be accessed HERE. Therefore, this platform is available worldwide (e.g. for general public use) on the CIIMAR website.

FIGURA

IN THIS HNS ONLINE PLATFORM, WE CAN FIND:

	Two online databases:

 Hazardous and Noxious Substances Spill Incidents;  Fate, weathering, behaviour and toxicity of priority Hazardous and Noxious Substances.

	Guidelines and protocols on environmental monitoring;
	Dissemination material (e.g. e-learning courses);
	Tools for the Portuguese coast (e.g. an environmental sensitive index).

FIGURA


This platform aims to support the preparedness and response to accidental spills (including Oil), in order to foster a more effective decision-making process.


2. Hazardous and Noxious Substances Spill Incidents - an online database


Information on previous spill incidents occurred at the sea worldwide involving HNS can be found in one online database (Hazardous and Noxious Substances Spill Incidents) elaborated by CIIMAR in the framework of the ARCOPOL plus project (Improving maritime safety and Atlantic Regions’ coastal pollution response through technology transfer, training and innovation).

To access this database: click HERE or select “HNS involved in former spill incidents” in the online platform.


FIGURA


In this online database, an ADVANCED SEARCH can be done. It is possible to use queries to search by SHIP NAME, name of the HNS SPILLED, YEAR when the spill occurred or INCIDENT LOCATION.

The database contains 187 entries of HNS spilled in 119 incidents in marine waters around the world.

For each incident, the information systematized is divided into the following points:  HNS Spilt  Fate and weathering facts observed/reported  Material Safety Data Sheets (MSDS) (attached when available) Example of the information systematized - case of BG Dublin incident:


FIGURA

Thus, information on the fate and weathering of HNS accidentally spilled at sea around the world was compiled in this database and, to this end:

	Data were analysed in terms of HNS physical behaviour in water according to SEBC (Standard European Behaviour Classification) code.
	The most common products involved in accidental spills in the marine environment were identified.
	Major lessons were highlighted. 

The article … More information on the methodology used to produce this online database as well as the results, discussion and conclusions (e.g. major gaps, priorities and recommendations) obtained can be found in the following article:

FIGURA

3. Fate, weathering, behaviour and toxicity of priority Hazardous and Noxious Substances - an online tool

Information on fate, weathering, behaviour and toxicity of priority HNS in seawater and shoreline environments can be found in an online database (Fate, weathering, behaviour and toxicity of priority Hazardous and Noxious Substances) produced by CIIMAR in the framework of the ARCOPOL Platform project. This public database was recently updated through the MARINER project (Enhancing HNS preparedness through training and exercising).

To access this database: click HERE or select “Fate, weathering, behaviour and toxicity of priority HNS” in the online platform.

FIGURA

In the database, it is possible to use queries to search by name of the HNS and behaviour at the sea.

FIGURA


Besides the substance name and the behaviour at the seawater, the priority HNS (24) - initially selected from the HASREP (2005) list of the 100 HNS most transported in European Atlantic waters - are also identified by their CAS number and formulae. 

FIGURA

Parameters compiled The parameters compiled in this database were as follows:

	Physicochemical properties / Characteristics

FIGURA


	Physicochemical degradation/Biodegradation

FIGURA

	Physicochemical degradation/Biodegradation


FIGURS

	Aquatic Toxicity


FIGURA

	Acute Mammals / Human health effects


FIGURA

	Chronic Mammals / Human health effects


FIGURA

	Toxicity tests results

PNECseawater • PNECwater intermittent

FIGURA For each HNS, most of the following toxicity parameters are available for four taxonomic groups (Algae, Invertebrates, Fish and Mammals – click on “Algae”, “Invertebrates”, “Fish” or “Mammals” to observe these toxicity results):

• EC50 (Effective concentration; 50%) • EC10 (Effective concentration; 10%) • EC3 (Effective concentration; 3%) • LC50 (Lethal concentration; 50%) • LD50 (Lethal dose; 50%) • ChV (Chronic Value) • LOEC (Lowest observed effect concentration) • NOEC (No observed effect concentration)


FIGURA


 LC50 (Median Lethal Concentration):  Statistically estimated concentration that is expected to be lethal to 50% of a group of organisms tested.  
 LD50 (Median lethal dose): The quantity of a chemical compound that, when applied directly to test organisms, is estimated to be fatal to 50% of those organisms under the stated conditions of the test. 
 ChV (Chronic value): Geometric mean of the LOEC and NOEC to characterize chronic toxicity.
 NOEC (No Observed Effect Concentration): The highest concentration of toxicant to which organisms are exposed in a full or partial life-cycle (short-term) test, that causes no observable adverse effects on the test organisms


FIGURA

The information compiled in this database was obtained from: • The literature (e.g. GESAMP list (2016)); • Several online databases (e.g. Environmental Fate Data Base (EFDB) from Syracuse Research Corporation (SRC)); • Mathematical/modelling tools - through the Estimation Programs Interface (EPI) Suite™, developed by the US Environmental Protection Agency's Office of Pollution Prevention and Toxics and Syracuse Research Corporation (SRC).

NOTE: IN A NEAR FUTURE, this database will evolve to incorporate more priority HNS, beyond the 24 selected presently, as well as more detailed (eco)toxicological endpoints as they become available.

The article …


More information on the methodology used to elaborate this online database as well as the results, discussion and conclusions (e.g. major gaps, priorities and recommendations) obtained can be found in the following article:


FIGURA

Link to MOHID HNS Spill Model Some toxicological data (e.g. LC50) present in this database and considered essential for the HNS risk assessment were linked to the MOHID HNS Spill Model , allowing the determination of potential effects on the marine environment.

4. Relevance of the online databases

The online database on previous incidents facilitates the incorporation of lessons from past incidents on the decision-making process to improve preparedness.

The public database on fate, weathering, behaviour and toxicity of priority HNS has the merit of assembling a brief and concise profile of 24 priority HNS. This database is a useful tool to develop more accurate HNS modelling tools and to predict the physicochemical behaviour of the priority HNS in accidental spills, also backing spill preparedness and effective decision-making process at the operational level. Additionally, this tool provides an important support to environmental and human health risk assessment (e.g. improve the predictions related to the potential hazards of HNS to the marine environment and associated resources such as fisheries, recreational areas, etc.), and monitoring actions.

Concluding, the information systematized in the online databases explained above (e.g. physicochemical and toxicological properties of HNS) is important to assist stakeholders involved in HNS spills preparedness and response (e.g. in the upgrading of HNS pollutant responses protocols and/or waste management protocols, etc.), policymakers and legislators. Moreover, these tools contribute to a current picture of the scientific knowledge on the fate, behaviour, weathering and toxicity of HNS, being essential to support future improvements in maritime safety and coastal pollution response before, during and after spill incidents.


References


Cedre (2009). Review of chemical spills at sea and lessons learnt. INTERSPILL 2009 Conference White Paper Technical Appendix. Marseille, France (40 pp.).

Cunha I, Moreira S, Santos MM (2015). Review on hazardous and noxious substances (HNS) involved in marine spill incidents - an online database. Journal of Hazardous Materials 285: 509-516.

Cunha I, Oliveira H, Neuparth T, Torres T, Santos M (2016). Fate, behaviour and weathering of priority HNS in the marine environment: an online tool. Marine Pollution Bulletin 111 (1-2): 330-8.

GESAMP Composite List (2016). ANNEX 5 – UPDATED GESAMP COMPOSITE LIST. Available at: https://edocs.imo.org/Final Documents/English/PPR 1-CIRC.3 (E).docx (accessed April 12, 2017).

HASREP (2005). Response to harmful substances spilt at sea. Prepared by the Alliance of Maritime Regional Influences in Europe (AMRIE) Centre de Documentation, de Recherche et d'Expérimentations Sur Les Pollutions Accidentelles Des Eaux. (CEDRE) and TNO Built Environment and Geosciences, The Netherlands (38 pp.).

Mayo-Bean K, Moran K, Meylan B, Ranslow P (2012). Methodology Document for the Ecological Structure-Activity Relationship Model (ECOSAR). Class Program. (30 p.) Available at: https://www.epa.gov/sites/production/files/2015-09/documents/ecosartechfinal.pdf (accessed April 13, 2017).

Neuparth T, Moreira S, Santos MM, Reis-Henriques MA (2011). Hazardous and noxious substances (HNS) in the marine environment: prioritizing HNS that pose major risk in a European context. Marine Pollution Bulletin 62: 21–28.

Neuparth T, Moreira SM, Santos MM, Reis-Henriques MA (2012). Review of oil and HNS accidental spills in Europe: identifying major environmental monitoring gaps and drawing priorities. Marine Pollution Bulletin 64: 1085-1095.

Modelling Fate & Behaviour of HNS Spills

Modelling Fate with MOHID and Modelling Population with Aquatox

Coastal Vulnerability Mapping

Vulnerability Mapping (e.g. risk management prioritization) and methodology.