Managing the Environmental Sustainability of Ports for a durable development
Roadmap on Sustainability Criteria:
Guidelines for Port Environmental Management
Executive summary The protection of the environment and the prevention of pollution scenarios are important competitive features for the whole Mediterranean basin. According to the general objectives of the ENPI CBC MED Programme, MESP project (Managing the Environmental Sustainability of Ports for a durable development) aims to reduce air, noise and water pollution in ports and nearby areas ensuring environmental -both natural and urban- sustainability of harbor activities and high level of life quality in surrounding territories. In this way, MESP aims to reach the identification of best practice and of procedures which can help the management authorities and the users of the port areas and infrastructures to reach an higher level of sustainability and to decrease the pollution level for what concern air and noise and water. The project aim is also the reproducibility of its results in order to create practices and procedure easily applicable in both side of the Mediterranean Sea. The following document “Roadmap on Sustainability Criteria: Guidelines for Port Environmental Management� represents the synthesis of this selection process and is intended to provide directions and advices for correct use and application of improvement methods to all Mediterranean Ports wanting to ensure a higher environmental impact of port activities and significantly improve life quality of the local populations.
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Table of contents MESP project .............................................................................................................................. 4 Aim of the document .................................................................................................................. 7 Pollution in ports and surrounding areas ................................................................................... 9 Approach criteria ...................................................................................................................... 12 Law and standard regulations. ............................................................................................. 13 Methodologies: general approach ........................................................................................... 15 Methods, skills and procedures ............................................................................................ 15 Approach to pollution problems .......................................................................................... 16 Methodologies: specific sector approach................................................................................. 18
................................................................................ 19 Definitions............................................................................................................................. 22 Basic measurement equipment............................................................................................ 24 Technical standards of measurements ................................................................................. 24 Measurement methodologies .............................................................................................. 26 Individuation of most critical sources................................................................................... 29 Reports.................................................................................................................................. 30
............................................. 32 Definitions............................................................................................................................. 35 Basic measurement equipment............................................................................................ 38 Technical standards of measurements ................................................................................. 41
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Measurement methodologies .............................................................................................. 44 Individuation of most critical sources................................................................................... 45 Reports.................................................................................................................................. 45
...................... 47 Definitions............................................................................................................................. 50 Basic measurement equipment............................................................................................ 50 Technical standards and methodology of the measurements ............................................. 51 Reports.................................................................................................................................. 56
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MESP project Managing the Environmental Sustainability of Ports for a durable development ENPI CBC MED – Cross-border cooperation in the Mediterranean Mediterranean Sea Basin Programme 2007-2013 Priority 2 Promotion of environmental sustainability at the basin level Measure 2.1 Prevention and reduction of risk factors for the environment and enhancement of natural common heritage Project in brief The intensification of maritime traffic, both in terms of goods and passengers, needs to be accompanied by an environmentally sustainable management of port areas so to reduce harmful consequences for local populations. MESP addresses the reduction of water, air and noise pollution deriving from port activities through the implementation of a multidisciplinary approach, which encompasses technological, regulatory and administrative solutions. The reinforcement of cooperation between port authorities, scientific organizations and public administrations will foster the diffusion and transfer in the Mediterranean area of sustainable management model of port areas developed by MESP project. Partnership
Beneficiary University of Genoa – DIME, Mechanical Engineering, Energy, Management and Transports Department (Genoa, Italy)
Physical Oceanography Marine Science Station (Jordan, Al-Aqaba)
La Spezia Port Authority (Italy, Liguria)
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Al-Manar University of Tripoli (Lebanon)
Municipal Enterprise For Planning & Development of Patras (Greece, Peloponnisos) Exploitation Office of the Port of Tripoli (Lebanon) Associated Partners Jordan Environment Society
Urban Community Al-Fayhaa
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Specific objectives To reduce pollution in concerned ports and nearby urban areas To reinforce the skills of public-decision makers and local administrators To develop certification tools, which allow to assess the level of environmental sustainability of port areas Expected results Identification of technologies for reducing and monitoring air, water and noise pollution due to port activities Definition of a standard model to improve the sustainable management of ports and application in 4 pilot areas Reduction of water, air and noise pollution in selected ports Improvement of the life quality of port users and local populations Harmonisation of procedures, methodologies and approaches in the Mediterranean Basin Target groups Public administrations staff Port authorities managers Scientific community Final beneficiaries Local populations Port operators Tourists Duration 36 months (starting from June 1st 2012)
Total budget: € 1.388.695,72 Programme contribution: € 1.249.826,15 (90%) Project co-financing: € 138.869,57 (10%)
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Aim of the document Many ports, especially in the Mediterranean area, are in very close proximity to the urban populated area and, often, are integral part of the city. It is well known that port areas contain sources of pollutants in different sectors (spill operation of large ships, merchandise handling to and from the port, cargo and passengers transport, large ships powering, sludge and sewage, goods handling inside the port) strongly impacting the environment of the surrounding area and, as a consequence, local population, port workers and tourists as well as both terrestrial and marine ecosystems. To contrast the poor knowledge about existing technology and procedures applied outside each partner territorial contest, preventing an homogeneous development of port infrastructures in Mediterranean basin and, above all, hampering the entry of new methodology and technologies which can absolve works with a large savings of energy and a substantial environmental pollution abatement, MESP project propose a roadmap on methodologies, good practices and measurements assessment for the environmental sustainability of ports. These guidelines aim to:
Provide regulatory systems and procedures for environmental local port governance processes Offer simple and best-practice approaches to a sustainable management of harbors, especially in the Air, Noise and Water sectors Offer efficient methodologies and technologies for the environmental pollution reduction; Identify suitable criteria and indicators for verifying the environmental sustainability of Mediterranean ports
They are addresses to: professional figures of Mediterranean basin port public administrations or responsible of harbor territorial management,
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scientific, operative and technical expertise on environmental pollution, in the specific about Air, Noise and Water scientific experts of the territory’s governance and common development strategies.
The document describes: The approach criteria of the proposed methodologies aimed to the environmental sustainability The basic principles to be followed for the pollution management of in port areas Specific procedures for the use of indicators, technical equipment and monitoring methods within the three sectors: Air, Noise and Water.
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Pollution in ports and surrounding areas European ports represent today the main door of access to enter Europe and MiddleEast territories for transports from all over the world. The strengthening of the motorway of the sea strategy by the EU aims to consider them not only as the main commercial platform, but also the main communication hub of the near future. In this sense, ports areas and authorities have to manage a situation more and more critical both from the point of view of sea and land traffic flows. Besides, the increasing of commercial traffics induces to a consequent implementation of land processing on goods while the increase of people traffics brings to several problems concerning with the “parking� of big cruise boats. The growth of sea traffic introduces critical points in terms of environmental sustainability concerning harbors as central location of import/export traffic removed from the road. Ports represent in this sense the most important and critical transit area between the sea and the city. The impacts of trade, industrial and construction activities as well as the auxiliary services concentrated in coastal areas, often on the border of a town center, can produce negative effects both to the natural eco-system and to the near resident urban population. Ports are characterized by a higher degree of complexity and variety of operations in comparison with other logistic nodes. The diversity of cargo types, the large range of activities, products and services taking place within the port zone, the multiple use of the areas and infrastructure have a deep impact on the urban and natural environment. In fact, in several cases port areas are situated in close juxtaposition to urban areas and may even be bounded by, or include, areas of special environmental significance due to the presence of protected habitats and ecosystems. All the activities carried out in harbors (industrial, trade, passengers and pleasure crafts) are actually relevant sources of pollution strongly affecting port areas and their users as well as bounding urban areas, which mostly in the Mediterranean basin
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result to be extremely close. Different fields are involved such as air, noise, water, lighting pollution, land use and landscape impact. Air, noise and water are the environmental components resulting most affected by the pollution caused by port activities and need to be strongly taken into consideration for a sustainable development of harbors. Concerning air sector, fine particles, fumes and gases from ship drains, auxiliary engines, truck emissions, harbor craft, terminal equipment are released in the atmosphere and carried inland by the wind. This affects the health of port workers and people living nearby causing health disease such as respiratory and cardiovascular issues. About noise pollution, the analysis results complicated due to the presence in the same area of several types of sound sources with different characteristics from each other, such as ferries, ships and trade operations, industrial and shipyards activities and well auxiliary services. In this way, noise pollution can produce negative effects both to the natural eco-system and to the urban population, causing negative effects and damages on human health (effect on hearing, cardiovascular disturbances, high blood pressure, sleep disturbance, reduction in efficiency, annoyance, mental stress, lack of concentration). Regarding water, port activities can have a strongly negative impact on the marine environment, causing long term significant damage and a critical effect both on
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marine wildlife and human health. Quality of sea water is affected form ballast and industrial wastewater, waste from ships, leaking oil from machinery and other toxic substances from vessels, litter, gaseous air pollutants, dust, hazardous materials, devastating to the aquatic ecosystems. In this sense, through these guidelines, MESP project aims to provide procedures and tools allowing objectively to value the sustainability of ports in order to reduce pollution sources in the Air, Noise and Water sectors and give back to citizen, tourist and workers an healthier and usable environment.
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Approach criteria In building the document “Roadmap on Sustainability Criteria: Guidelines for Port Environmental Management� specific cross-cutting criteria have been chosen in order to approach the environmental and sustainable improvement and management suitable for all ports areas. In fact, beyond the peculiarities of the different pollution fields, there are actually some essential key concepts at the basis of the procedures in common among all. These criteria, indeed, relate to the general approach to the pollution issue and can be applied a priori to any port context. The selected criteria are listed as follows:
1. Simple attitude. As a first approach to the environmental issue, especially in a complex environment such as a port area, the vision to face the problem must be particularly simple in order to straightly focus on the target goal and achieve it in the clearest way. 2. Simple methodologies. Similarly to the previous point, the methodologies should be simple as well, by following the use of a simplified EMS (Environmental Management System), limiting the staff involvement, the time consumption and the budget resources. In-depth technical activities may be useful in an advanced stage of the analysis, namely if the pollution scenarios cannot be solved otherwise or environmental issues are originated by particular contexts. 3. Simple indicators. The indicators, which are the means by which the level of environmental pollution assessment can be evaluated and the strategies for the analysis and the control of pollution can be estimated, in the first steps do not have to be complex and must show a general scenario snapshot of the port context.
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4. Effective examples. Methodologies, technologies and practices will have to be based on a database and a catalogue of examples and best practices concerning pollution values abatement and port environment management. 5. Interference within the port area. Measurements or interventions for the environmental pollution reduction must not disturb and/or interfere with the normal operation of port activities. 6. Identification of dominant environment issues. Before defining any kind of method and procedures it is necessary to identify all the environmental problems affecting the port area. The evaluation process should face the effects induced both globally and on each single environmental component (i.e. air, noise and water) identifying the main sources as well as the main areas exposed and the responsible subjects for priority actions. For a more accurate environmental analysis, it could be useful considering additional information for the evaluation of the environmental impact concerning the characteristics of nearby areas (urban, peri-urban, sub-urban, etc.) and the frequency and/or periodicity of certain specific activities as tourism (passenger cruise) and pleasure crafts use which strongly depend on the season.
Laws and standard regulations. The methodologies to be applied in the assessment of the environment pollution impact should first of all respect the national laws scenario. The regulatory background in which the monitoring activities have to take place is essential to obtain an holistic approach in the evaluation and management of environment quality in order to:  
identify the objectives for environment quality designed to avoid, prevent, reduce harmful effects on human health and the environment as a whole; assess environment quality on the basis of common methods and criteria;
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collect information on environmental quality as a basis for identifying the measures to be taken to fight pollution and the harmful effects of it on human health and the environment and to monitor long-term trends; maintain of environment quality if itis good; guarantee to provide public opinion with accurate information on ambient air quality.
In pollution monitoring, first of all local or national laws and standards need to be identified and selected in order to clearly define the limits of pollutants and measurement procedures.
If the subject’s country is an EU member state, specific EC requirement are needed either for measurement methods or for the equipment needed.
If the subject’s country is not an EU member state, the standards of reference are represented by the available worldwide regulations from international standards organizations (e.g. US-EPA in case of air, ISO standards in case of noise, etc.).
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Methodologies: general approach Methods, skills and procedures As for the criteria previously described, some common method, skill and procedure features for the environmental improvement of port contexts have been identified for the three topics and, eventually, have been analyzed in a unique way, as described as follows: 
Assessment of current pollution context within the harbor area -and in the surrounding urban territory- including landbased and vessel operations through measurements campaign (see below), site visits and interviews with port officials, port operation managers, on-site inspection of the port area, interviews with the local involved institutions (Port Authority, Municipality, Government, etc.), stakeholders and ship captains.
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Collection of useful information such as GIS map of the area, geographical boundaries of the project, proximity of residential and industrial areas from harbour pollution sources, historical meteorological data, complaints from population and harbour workers, medical records (e.g. health issues, diseases, etc.), companies and other noise sources like transport, ship moored, installations, etc.
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Identification of different pollution sources and their generation mechanism, in order to better focus on the reduction actions trough environmental monitoring actions allowing at the same time.
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Environmental monitoring actions as an essential tool for a sustainable development of ports and other productive urban areas by evaluating the respect of fixed normative limitations. In addition, they could give constant and update information on pollution level values concerning all different components (air, noise, water, etc.). Monitoring activities have a crucial role in the success of an action or process especially in the long-term period, as a key point for the sustainable development.
Operator skills. Measurement for the evaluation of the pollution level of the port scenario have to be carried out by environment specialists with a complete knowledge of the use, measurement procedures and calibration of the equipment in order to ensure the accuracy of the results.
Approach to pollution problems In the same way, a common approach to the pollution problems can be followed within the different sectors. In fact, the line methodology for Air, Noise or Water sectors generally includes the following steps: Scope: Evaluation of the goals and purpose. Methodology: Planning and development of the approach in the pollution reduction. Action: Implementation of activities. Check: Verification of target achievements and/or correction if needed. Particularly, the pollution reduction procedures contain multiple steps:
Identification of the pollution problems within the port area and determination of indicators limits according to national and international standards.
Pollution assessment through monitoring campaigns, in order to identify pollution sources, detect pollution trends and find out critical areas exposed to pollution levels higher than standard values.
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Evaluation of the sensitive objects (hospital, school, etc.) and number of exposed people.
Priorities establishment, by ranking pollution sources taking also into consideration the risk on human health, aquatic life and wildlife, the public interest and the importance of the port.
Pollution abatement action plans, to be developed from the monitoring survey results, containing target activities to implement in order to decrease the pollution levels. If possible, pollution and conflict map should be drawn up to better achieve the abatement goals. Additional actions may be: training on pollution awareness for port workers, improvement of the infrastructures (surface design and maintenance) and protection devices for employees where necessary.
Assessment monitoring in order to evaluate the effectiveness of the action plan measures and determine whether pollution standards have been attained or more stringent controls should be applied.
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Methodologies: specific sector approach Specific key elements related to its own sector have to be focused, as shown in the following pages, on the analysis of different aspects of the specific topic issues: Air, Noise and Water. For each pollution sector, the following aspects are specified:
definition of the most significant indicators to be considered and evaluated basic measurement equipment to use in order to carry on proper measurement campaign technical standard and procedures of measurement to be followed measurement methodologies to adopt for the pollution sources identification individuation of the most critical sources reports containing information on the collected data.
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Port activity, especially when providing the handling of bulk goods, produces unavoidable impacts on air quality within the surrounding area, due to the dispersion of powders -especially fine particles- fumes or gases. Strict monitoring programs about air conditions are already being implemented in several harbors, in order to identify possible violations of law-limits related to concentrations of fine particles, whose adverse health effects have been proved. Some of the actions to be taken and continuously implemented in order to reduce adverse effects on environment and health can be represented by projects regarding reduction of road traffic in favor of railway, improvement of combustion processes in combustion engines and progressive replacement with electric motors or low emission of harmful gases (NO2, CO, CO2, etc.), frequent cleaning of the streets and squares with appropriate sweepers, continuous monitoring of concentrations of particulate matter and total dust in air. Therefore, projects facing control, scientific and standardized parameters of air quality must find the support and active participation of all the institutional bodies and business that are involved in the handling of goods, in order to identify new and more effective measures to prevent and mitigate the spread of dust in the environment, within a framework of sustainable development of ports.
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The first step in the identification of the most suitable methodologies to be applied to improve the environmental sustainability of ports within the Air topic should consider the following actions:
The assessment of: - Dry bulk storage and handling - Liquid bulk storage and transfer (Loading/Unloading) - Non-bulk chemical storage and handling - Port cargo handling equipment and truck operations powered by diesel engines - Vehicle and equipment fuelling - Management of hazardous and non-hazardous waste - General operations that can impact surrounding urban areas - Buildings and grounds maintenance The determination of the pollutants mostly affecting the environmental sustainability. The consideration of emissions (air pollution, odour originating from a facility or source) and immissions (defined as effects of air pollutants on plants, animals, on human beings and on the atmosphere).
The second step foresees the collection of useful resources and data that can be helpful during the analysis and the evaluation of the action to be implemented. Specifically, the needed information is:
Concerning the reduction of the negative impacts of port general operations (such as, e.g., dust from dry bulk storage piles, cargo loading/unloading and maintenance/use of dirt/gravel roads on port): - Type, quantity, duration of storage and frequency of piles - Port road information: length, surface, coverage material, etc. - Current road projects - Equipment used within the port Concerning the pollutants from diesel exhaust emitted by land-based equipment and vessels and vapours from transfer of liquid bulk products: - CORINAIR or EPA Standards - Type of equipment and related impact - Frequency of vessels in the port - Type of diesel used - All other information required by standards
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Concerning trash from port activities, “dumped” outside port area by visitors, service providers, employees, others: - Activities generating trash - Nature - Quantity Concerning traffic congestion from truck queuing, security checks, service deliveries, etc.: - Port operation schedule - Number of trucks entering the port/queuing in front of entrance - Any past data or statistics regarding trucks
In order to ensure the proper execution of measures campaigns and monitoring activities, some information on the measurement methods, on the investigated parameters, on data collection and on the technical equipment to be used in the topic Air are required. A good approach in this area is, in fact, essential in order to obtain valid results and, thus, to ensure the maximum accuracy in the subsequent intervention actions.
Definitions Particulate Matter (PM10): Particulate Matter (PM) is a mixture consisting of solid and liquid particles having different chemical and physical characteristics – small enough to be suspended in the atmosphere. In particular, PM10 means particles up to 10μm in size. Particulate Matter comes either from natural sources (such as, fire, soil erosion, evaporated sea spray etc.) or anthropogenic sources, mainly urban traffic and combustion processes. It can be emitted directly into the atmosphere (primary pollutant) or develop from chemical reactions or condensing processes. The length of time the particulate matter remains in the atmosphere depends on the particle size as well – as finer particles tend to be suspended for a significant amount of time, therefore, to spread evenly on vast areas. Nitrogen Dioxide: mainly, Nitrogen Dioxide (NO2) is a secondary pollutant which develops from oxidation of nitrogen oxide (NO) – these two compounds are globally known as Oxides of Nitrogen (NOx). The Oxides of Nitrogen are emitted directly into the atmosphere following high temperature combustion processes (heating plants, car engines, industrial combustion, power plants, etc.) due to oxidation of the
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atmospheric nitrogen and - only at a small extent – due to oxidation of the nitrogen compounds contained in fuels. Concerning road traffic, the highest amount of these pollutants is detected when the vehicles are running at full speed or accelerating, since the NOX production increases with the increase of the air/fuel ratio, to say, when there is the largest amount of oxygen available for combustion. Upon emission, most Oxides of Nitrogen are NO, with a NO/NO2 ratio definitely in favor of the first compound (in the emissions, the NO2 content is approx. 5 to 10% of the Total Oxides of Nitrogen) which is then oxidized in the atmosphere by the oxygen and more quickly by the Ozone, thus forming Nitrogen Dioxide. Nitrogen Monoxide is not regulated, since at the typically-measured ambient air levels it has no harmful effects on human health and/or the environment. Nevertheless, its levels are measured because – through its oxidation into NO2 and its involvement into other photochemical reactions – it plays a role in the production of Tropospheric Ozone (O3). Ozone: the Tropospheric Ozone (O3) is a secondary pollutant formed from chemical processes that occur in the atmosphere – driven by ozone precursors, namely, Oxides of Nitrogen and Volatile Organic Compounds (VOCs). Such reactions are facilitated by intense sunlight and high temperatures and result into the formation of different pollutants (photochemical smog). Typically, Ozone pollution occurs in summertime, with highest concentrations detected in the afternoon at suburban areas located downwind from urban industrial zones. Carbon Monoxide: Carbon Monoxide (CO) is a gas emitted from vehicle tailpipes or propulsion systems where an incomplete combustion of fossil fuels occurs. The main sources of CO emissions include cars, trucks, motorcycles, and some industrial processes. High concentrations can be found in enclosed spaces, such as garages, poorly-ventilated tunnels or along the roads affected by heavy traffic. Other pollutant: further standard air pollutants that can be analyzed in compliance with European Community standards can be:
BTX SOX PM2.5
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Basic measurement equipment A complete air pollution monitoring equipment set must contain, at least:
Carbon Monoxide Analyzer Ozone Analyzer Nitrogen Oxide Analyzer Air sampling unit (to be placed 4.5m above the ground) Automatic Calibration System by means of low-concentration cylinders Automatic Analyzer for continuous monitoring of airborne particulate, equipped with a PM10 sampling head (to be placed approximately 5m above the ground) and a microprocessor to control a sequential sampling unit Stand-alone Pump equipped with a microprocessor to control a sequential sampling unit Sequential Sampling Unit, to control the filters in auto mode Weather Transmitter, mounted onto a telescopic pole mast of 10m approximately Data Acquisition system, (PC, Ethernet Switch, GSM modem for sending data to the Master Control Station) Sampler Automatic Analyzer for continuous monitoring of airborne particulate, equipped with a PM10 sampling head (approximately 5m above the ground) and a microprocessor to control a sequential sampling unit
Technical standards of measurements For the determination of the different parameters of air quality it is suggested to adopt quality objectives and to detect appropriate reference methods and any equivalent methods in order to ensure maximum comparability in measurements( for example, the methods used in La Spezia’s sites are described in the following).
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However, given the heterogeneity of the participants in the MESP project, it is considered appropriate to achieve shared methods in order to ensure the comparability of results and, where they are non-reference methods, it is important to acquire a demonstration of equivalence.
Reference method for nitrogen dioxide and oxides of nitrogen The reference method for the measurement of nitrogen dioxide and oxides of nitrogen is that described in EN14211:2005 ‘Ambient air quality — Standard method for the measurement of the concentration of nitrogen dioxide and nitrogen monoxide by chemiluminescence’.
Reference method for PM10 The reference method for the sampling and measurement of PM10 is that described in EN 12341:1999 ‘Air Quality — Determination of the PM10 fraction of suspended particulate matter — Reference method and field test procedure to demonstrate reference equivalence of measurement methods’.
Reference method for PM2,5 The reference method for the sampling and measurement of PM2,5 is that described in EN 14907:2005 ‘Standard gravimetric measurement method for the determination of the PM2,5 mass fraction of suspended particulate matter’.
Reference method for Carbon Monoxide The reference method for the measurement of carbon monoxide is that described in EN 14626:2005 ‘Ambient air quality — Standard method for the measurement of the concentration of carbon monoxide by non-dispersive infrared spectroscopy’. Reference method for Ozone The reference method for the measurement of ozone is that described in EN 14625:2005 ‘Ambient air quality — Standard method for the measurement of the concentration of ozone by ultraviolet photometry’.
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Measurement methodologies Data quality objectives In order to have proper populated dataset, it is suggested the adoption of quality objectives which provide for the validation of the collected data a minimum number of samples and the determination of the uncertainty on the same. As an indication, the following table lists those required by current Italian regulations for indicative measurements (i.e. not fixed monitoring sites, like in this monitoring project) and applied in the course of these campaigns. Nitrogen dioxide and oxides of Particulate matter nitrogen, carbon monoxide (PM10/PM2,5)
Ozone
Measurements indicative error
25%
50%
30%
Minimum data
90%
90%
90%
The minimum requirements for the collection of valid data and the minimum time coverage do not include losses of data due to the regular calibration or the normal maintenance of the instrumentation, where such activities are conducted in accordance with the quality assurance programs.
Identification of monitoring parameters and points The rules to define measurements clearly depend on polluting and on the source to be monitored. It should also be pointed out that the minimum number of measurement points is not in itself a guarantee of the ability to adequately represent the state of air quality, and is therefore a necessary but not sufficient condition for a complete monitoring of the situation in a the area. The intent is in fact trying to define a minimum level of evaluation, rather than a maximum level. Two main areas can be identified, as a result of the boundary conditions in terms of morphology topography, characteristics of the settlement, and level of complexity of the port site:
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Macro scale. The measuring stations must be located as to be as much representative as the sampling ones. including those not located in the immediate vicinity. Hence, air quality assessment conducted in the sampling site, can be considered to be representative of air quality even in similar areas.. Micro scale. The measuring stations is suggested to apply the following criteria on micro scale siting that are dictated by the rules of common sense. - the flow around the inlet sampling probe shall be unrestricted (free in an arc of at least 270°) without any obstructions affecting the airflow in the vicinity of the sampler (normally some metres away from buildings, balconies, trees and other obstacles and at least 0,5 m from the nearest building in the case of sampling points representing air quality at the building line; - in general, the inlet sampling point shall be between 1,5 m (the breathing zone) and 4 m above the ground. Higher positions (up to 8 m) may be necessary in some circumstances. Higher siting may also be appropriate if the station is representative of a large area; - the inlet probe shall not be positioned in the immediate vicinity of sources in order to avoid the direct intake of emissions unmixed with ambient air; - the sampler’s exhaust outlet shall be positioned so that recirculation of exhaust air to the sampler inlet is avoided.
The following factors may also be taken into account:
interfering sources, security, access, availability of electrical power and telephone communications, visibility of the site in relation to its surroundings, safety of the public and operators, the desirability of co-locating sampling points for different pollutants, planning requirements.
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Documentation and review of site selection The procedures for selection of fixed sampling sites should be fully documented, for example by photographs of the surrounding environment in the direction of north, south, east, west, and detailed maps. The selection should be reviewed at regular intervals with repeated documentation to ensure that selection criteria remain valid over time.
Operational measures for mitigating the impact of port activities A number of possible actions have been identified, some of a more general nature, and others to be activated, for example, to the overcoming of the threshold values and critical levels (to be defined for each site and for each parameter) of the air quality. use of renewable energy where possible; use of environmental friendly technologies and alternative materials to conventional (for example with the use of bases with the photo catalytic titanium dioxide); application of environmental engineering and green building techniques where possible; cold ironing, thanks to which the vessels are plugged into the dock does not have to keep their engines running to power the auxiliary generators on board, resulting in substantial savings in terms of emissions and also strong reduction of noise pollution; creation of portals spray, real gaps with dust extraction systems of transport in and out of the harbour; reduction of dust including the harbour refitting by wind through a systematic and organized action of cleaning the roadways and yards and treatments with biological fixing products that, thanks to an active enzyme consists of natural organic molecules with a high molecular weight, are able to trap fine dust; use of fuels with low sulphur content; identification of actions to limit emission and dispersion of dust from powdered goods (e.g. improvements buckets, conveyor belts); reducing the impact of heavy traffic and private, through interventions both regulatory and structural traffic (use of rail transport);
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adoption of best available technologies for collecting and reducing emissions from activities as painting and sandblasting; apply a specific dispersion model that identifies the areas of greatest impact due to the sources listed in the register of emissions. Weather Parameters Meteorological parameters must measure the following factors:
Wind speed and direction Rainfall Atmospheric Pressure Temperature Relative Humidity
The technologies used for measuring each parameter could be the following:: Wind: Wind speed and direction sensors must detect the horizontal speed and direction of wind, with measuring range for wind speed from 0 to 60 m/s and wind direction measurement range from 0 to 360 degrees. Rainfall: Acoustic based measurement can be adopted. Detecting every individual raindrop as it impacts on the sensor surface, the system analyze the signal generated by raindrop impact, proportional to the volume of the raindrop itself. Then the signal from each raindrop can be converted into the accumulated quantity of rain. Atmospheric Pressure: The Atmospheric Pressure sensor must have minimal hysteresis and repeatability features. The measuring range must be from 600 to 1100 hPa. Temperature: it must have a measuring range from -50 to +60°C. Relative Humidity: it must feature long-term stability in a wide range of environmental conditions and negligible hysteresis and have a measuring range from 0 to 100%RH.
Analysis of most critical sources In the framework of the activities of air quality management and limits the emissions of pollutants into the atmosphere, it is important to obtain qualitative and quantitative information on emissions from different types of sources.
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In this context, the emissions inventory is intended as a collection, made in accordance with procedures and methodologies verifiable, updatable information and technological, economic, territorial data, which allows to identify the sources of pollution, their location with provincial and municipal disaggregation and the amount and type of pollutants emitted. The methodology suitable for the realization of an emission inventory provides the direct quantification, by means of measurements, of all emissions of different types of sources for the area and the period of interest. The "analytical" approach, however, is effective only for certain specific types of pollutants (e.g. Sulphur dioxide, nitrogen oxides, carbon monoxide) and of sources, typically large industrial plants (e.g. power plants, incinerators, cement plants) whose emissions are generally very relevant and controlled through this system of continuous monitoring. It is therefore necessary to resort to the approach used by most emission inventories, which estimate emissions on an indicator that characterizes the activity of the source and an emission factor specific to the type of source, process and industrial purification technology adopted. This method is therefore based on a linear relationship between the activity of the source and the issue. Within an emissions inventory could be divided into the following types:
spread, distributed over the territory, estimated through the use of appropriate indicators and emission factors;
spot, geographically localized pollution sources, estimated from the measured data collected through a special inventory, for some pollutants, non-monitored, emissions can result from estimation carried out as above;
linear such as roads, estimated through the use of appropriate indicators and emission factors, usually via methods of detail.
Reports The results should be presented in a separate report containing: a description of assessment carried out activities; the specific methods used, with references to descriptions of the method;
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 the data collected and presented in summary form with graphical comparisons with any series (including other neighbouring stations correlated);  analysis of the limits of the activity and the difficulties encountered.
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Ports and harbors are characterized by very several and complex operations, especially if compared with other logistic nodes. This make them an important source of pollution mainly when ports are localized very close to urban areas. Particularly, noise pollution analysis is complicated due to the presence in the same area of several types of sound sources with different characteristics from each other. Noise from ports areas, in fact, come not only from ferries and ships and trade operations (engines and ventilation systems, embarking-disembarking actions) but also from industrial and shipyards activities (repair shipyards, noise from operations on hulls in dry docks) as well auxiliary services (such as transshipment containers and trailer trucks handling noise, in particular due to the impacts during positioning, cranes sound warning devices, power plants) localized in the piers and docks of the port area. In this way, noise pollution can produce negative effects both to the natural eco-system and to the urban population, causing negative effects and damages on human health. To assess and manage the environmental port noise, several actions and solutions have to be studied and applied, in order to allow the development of trade without compromising the quality of life in port cities. Since in ports there are several noise sources typologies, the noise characterization in this ambit should be optimized through environmental acoustical monitoring plans that assume in this context a relevant role especially considering the effects induced on the near residential area. Monitoring plans, in fact, should be developed in order to identify through phonometric measurements the most critical noise zones and recognize the causes that have produced them, to acoustically characterize the sound sources (sound power, spectral characteristics, duration) and evaluate what kind of measurement methodology to use for characterizing them and the number of people harmfully effected. Then, the knowledge of the specific territory should allow the activation of operative actions with the aim of improving the acoustical comfort of critical areas. A particular importance has the choice of acoustic descriptors and indicators, useful to correlate the sound pressure level measurements, the percentage of persons who have negative effects on their health and to assess the damage caused by noise in the exposed population. Therefore, only in this way, management actions against noise in port areas can be planned and developed by improving procedures, policies, tools and intervention priorities can be fixed.
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As seen for Air topic, as a first step different actions for the identification of the most suitable methodologies to be applied to improve the environmental sustainability of ports within the Noise topic have to be considered: 
The assessment of: -
Port services and facilities, Vehicle noise: engine, exhaust, trucks, cranes, ships, Loading/unloading equipment Construction activities Maintenance activities Scrap merchandise Management of hazardous and non-hazardous waste General operations that can impact surrounding urban areas Building and grounds maintenance
The second step foresees the collection of useful resources and data that can be helpful during the analysis and the evaluation of the action to be implemented. Specifically, the needed information is: 

Concerning the reduction of the negative impacts of port general operations (such as, e.g., Cargo loading/unloading and maintenance/Vehicle noise/Construction and Maintenance activities): - Intensity and duration of all sources generating noise at the Port - Current road projects - Equipment used in the port Concerning the traffic congestion from truck queuing, security checks, service deliveries, etc.: - Port operation schedule - Number of trucks entering the port/ queuing in front of entrance - Any past data or statistics regarding trucks
It must be highlighted that it is particularly important, for the Noise topic, to consider during the measurement the evaluation of the multiplicity of sources generating noise within the harbour area (different noise pattern, sound power level, intensity
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and time duration) and the background noise deriving from, e.g., highways, urban roads and railways. In order to ensure the proper execution of measures campaigns and monitoring activities, some information on the measurement methods, the investigated parameters, data collection and the technical equipment to be used in the topic Noise are required. A good approach in this area is, in fact, indispensable in order to obtain valid results and, thus, to ensure the maximum accuracy in the subsequent intervention actions.
Definitions Specific source: identifiable sound source that is the cause of potential noise pollution. Reference time (TR): period of the day in which the measures are performed. The 24 hours are divided into two parts: from 06:00a.m. to 07:00 p.m. (day), from 07:00 p.m. to 10:00 p.m. (evening) and from 10:00 p.m. to 06:00 a.m (night). Long-term time (TL): sufficiently large period within the TR in which significant values are evaluated. The TL duration is related to the factors variations of that could influence the noise level on the long term. Observation time (TO): time period included in the TR in which occur the noise conditions to be evaluated. Measurement time (TM): within the TO, one or more TMs -with duration equal to or less than the TO- are identified, depending on noise characteristics and variability, in order to have representative measures. A weighted sound levels: LAS, LAF and LAI. These sound levels are the logarithmic mean effective values of the A weighted sound pressure level LPA, referred to the “slow”, “fast” and “impulse” time constants. A weighted maximum sound levels: LASmax, LAFmax and LAImax. These sound levels are the maximum values for the A-weighted sound pressure level LPA, referred to the “slow”, “fast” and “impulse” time constants.
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A-weighted Equivalent Sound Level (LAeq): energy average A-weighted sound level occurring over a given time interval (t1 - t2). A-weighted Equivalent Continuous Sound Level (LAeq,T): energy average A-weighted sound pressure level of a constant sound that, in a specified period T, has the same quadratic average pressure of a known sound with T variable level. [
∫
]
where: pA(t) is the instantaneous value of A-weighted sound pressure level in Pascal (Pa); p0 = 20 µPa is the reference sound pressure. A-weighted Equivalent Continuous Sound Level in the long-term time TL (LAeq,TL): it can be referred to: a) the average value over the whole period: [ ∑
(
)
]
where:
N are the considered reference times
The individual period in the TR. In this case, it identifies a 1 hour wide TM inside the TO in which the phenomena in exam takes place. The LAeq,TL represents the A-weighted equivalent continuous sound level resulting from the sum of the Ms TM measurement slots. It is the level to be compared with the limits and is expressed by:
[
∑
(
)
]
where:
i is the single 1 hour period in the ith TR.
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13-hour day-time A-weighted Equivalent Sound Level (LD): the acoustic describer referred to the period from 06:00 a.m. to 07:00 p.m. 3-hour evening-time A-weighted Equivalent Sound Level (LE): the acoustic describer referred to the period from 07:00 p.m.to 10:00 p.m. 8-hour night-time A-weighted Equivalent Sound Level (LN): the acoustic describer referred to the time period from 10:00 p.m. to 06:00 a.m. Day-evening-night A-weighted Equivalent Sound Level (LDEN) (
)
Sound exposure level SEL (LAE): it quantifies the total A-weighted acoustic energy integrated over a time interval for a given acoustical event. Simplifying, the SEL of an event is described as the hypothetical equivalent sound pressure level enduring for a period of one second that would have the same amount of acoustic energy as the specific transient event for which the SEL was measured and is expressed by: [ ∫
]
where
t2 and t1 is a period sufficiently wide to enclose the event; t0 is the reference duration (1 s)
Environmental Noise Level (LA) is the A-weighted equivalent continuous sound pressure produced by all the noise sources in a given place and in a certain period. The environmental noise is made up of residual noise and of specific disturbing sources, with the exception of the well identifiable unusual events. It is the level to be compared with the maximum limits of exposure: 1) in the case of differential limits, is reported to the TM 2) in the case of absolute limits is referred to the TR Residual Noise Level (LR) is the A-weighted equivalent continuous sound pressure detected when the specific disturbing source is excluded. It has to be measured with the same methods used for the measurement of environmental noise and must not contain atypical sound events.
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Differential Noise Level (LD): it is the difference between the Environmental Noise Level (LA) and the Residual Noise Level (LR):
Emission level: it is the A-weighted equivalent continuous pressure sound level due to a specific source. It’s the level to be compared to the emission limits. Correction factor (Ki) is the correction in dB(A) which consider impulsive, tonal or low frequency components:
presence of impulsive components Ki = 3 dB presence of tonal components Kt = 3 dB presence of low frequency components in Kb = 3 dB
The correction factor is not applied to transport infrastructure. Presence of non-continuous noise: the presence of non-continuous noise is considered -only during the “day” TR- in case of noise duration equal or less than one hour. If the noise duration is less than one hour, the value of environmental noise, measured in Leq(A) must be reduced by 3 dB(A); if it is less than 15 minutes the Leq(A) must be reduced by 5 dB(A). Corrected Noise Level (LC) is defined by:
Basic measurement equipment Measuring system The measuring system should be chosen in order to satisfy the specifications established for class 1 in EN 60651/1994 (replaced by EN 61672-2/2003) and EN 60804/1994. The data of equivalent level must be carried out directly with a sound level meter according to class 1 of EN 60651/1994 and EN 60804/1994. Class 1 provides the required accuracy for the measurement of environmental noise.
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Filters and microphones Filters and microphones used in the measures must satisfy EN 61260/1995 (IEC 1260) and EN 61094-1/1994, EN 61094-2/1993, EN 61094-3/1995, EN 61094-4/1995. Calibrations Calibrators must be conform to CEI 29-4. The full measuring system must be controlled with a class 1 calibrator according to IEC 942/1988 before and after each measuring cycle. Acoustic measurements are valid if the gap before and after each measurement cycle is less than 0.5 dB. In case of recording and playback, the calibration signals must be recorded. Tools and measurement systems shall be provided with a certificate of calibration and checked at least every two years to verify compliance with the technical specifications. Other In case of use of other elements to complete the measurements and everything else not specified, it must be ensured that said elements respect limits of tolerance for the class 1 mentioned above. Accessory elements Tripod Microphone windscreen Data collection form (as shown in the following picture)
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Noise Measurement Campaign [Insert here the name of the place you are having measurement] 2
Data File Name : Position no.:
3 4 5 6 7 8 9 10 11 12 13 14 15
Measure position : Adress - City/Town Date - Time - Day Reference time Measurement technician Air Velocity - Temp. - Humidity Sound Level Meter model Leq L 90 L 95 L 99 L I max L S max
: : : :
m/s
째C
%
: :
dB(A)
:
dB(A)
:
dB(A)
:
dB(A)
:
dB(A)
:
dB(A)
Notes :
16
17
:
Leq Noise Spectrum
18
Picture of the measurement position
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Technical standards of measurements Prior to any measurement campaign, it is necessary to acquire all the information that may affect the choice of the method, times and locations of tests. The noise measurements should consider variations in the emissions and the propagation of sound sources. All the data leading to a description of sources affecting the environmental noise in the investigated area have to be collected. If recognizable, it is important to indicate the major noise sources, the sound level variability and any tonal and/or impulsive and/or low frequency components. The measurement of A-weighted equivalent continuous sound pressure level in the period of reference (LAeq,TR): ∑ can be performed: a) Continuous integration method. The LAeq,TR value is obtained by measuring the environmental noise during the whole reference period, with the possible exception of time slots in which anomalous conditions occur, being not representative of the area. b) Sampling method. The LAeq,TR is evaluated as the average of the A-weighted equivalent continuous sound pressure level values, related to the time of observation (TO). The value of LAeq,TR is given by: [
∑
]
The measurement methodology records value of LAeq,TR representative of the environmental noise scenario in the TR, the studied area, the source type and noise propagation. The measure must be rounded up to 0.5 dB. In free field measurement campaign, has to be oriented towards the source of noise. If the source is not localizable or there are multiple sources, a microphone with random incidence must be used. The microphone should be fixed on a support and
41
connected to the sound level meter with cable long enough to allow operators to stay at least at 3 m away from the microphone. In case of buildings with façade flush with the road, the microphone should be placed at 1 m from façade. Otherwise (not flush or buildings in open spaces), the microphone should be placed inside the building and, in any case, not less than 1 m from the façade. The height of the microphone should be chosen in agreement with the actual or assumed position of the receiver. When measuring in free field, the microphone should be at a height of 1.5 m above ground surface. When measuring at 1,5m above the ground surface then corrections are needed (±1 dB). The shielding of local objects that can affect the outcomes of the noise measurement carried out at a short distance must be taken into account . Noise monitoring campaigns could be implemented as grid points (Colenbrander Method). The measurements should be conduct on the grid points with distance less than 0.2 d (d = the largest diameter of the objects situated in the matrix). If a point of the grid noise measurement cannot be carried out because not (objects, buildings, etc.) the value of the virtual point should be determined by means of extrapolation or interpolation taking into account that noise levels are logarithmic (not linear) values.
The measurement campaigns have to be done in absence of rainfall, fog and/or snow; the wind speed must not be more than 5 m/s and the microphone must be provided of windshield. The measuring system must be compatible with the weather in which measurements are made and in any case according to CEI 29-10 and EN 60804/1994.
Impulsive events instrumental survey In order to identify impulsive event, LAimax and LASmax levels for a suitable time have to be measured.
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Noise is considered having impulsive components when:
the event is repetitive; the difference between LAimax and LASmax is more than 6 dB; the event is less than 1 s at -10 dB from the value LAFmax.
The impulsive event is repetitive when occurs at least 10 times per hour during the daytime and at least 2 times per hour during the night. The repetition shall be demonstrated through graphic recording of LAF during the measurement time. The LAeq,TR level is increased by a correction factor KI as earlier defined.
Tonal components identification In order to detect presence of tonal components in the noise (CT), a 1/3-octave frequency bands spectral analysis has to be performed. Only stationary in time and frequency CT are considered. If sequential filters are used, the minimum of each band with “fast” time constant has to be determined. If parallel filters are used, the level of the stationary spectrum is highlighted by the lowest level in each band. In order to highlight a CT located at the crossover frequency of two filters at 1/3-octave, filters with greater selective power or alternatives crossover frequencies can be used. The analysis has to be carried out in the frequency range between 20 Hz and 20 kHz. A CT occurs if the minimum level of a band exceeds the minimum levels of the adjacent bands for at least 5 dB. The correction factor KT is applied, as earlier defined, only if the CT touch an isophonic curve equal or higher than the highest reached by the other components of the spectrum.
Low frequency components If the performed frequency analysis reveals a CT and the corrective factor KT in the frequency range between 20 Hz and 200 Hz has to be used, the corrective factor KB as earlier defined has to be applied, exclusively during the night time period.
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Measurement methodologies Measurement is a very important phase to know the airborne noise radiated from a ship, according to its operating condition. In order to deduce useful information to characterize the noise within a port context, the measurement campaigns must be articulated as follow:
long time (whole day/evening/night, preferably on several days) monitoring, in a significant site for the port noise immission, so as to have a wider overview and to possibly highlight both discontinuity and repetitiveness or frequency of the noise on the long-term. measurements on short time (e.g. 30-45 min) in different days and time slots, day and night-time, both in the same site (as in the continuous monitoring) and other sites in the study area, which provide information on the short-time noise level at different times and with different port scenarios. The number of measurements depends on the variations: if, after measuring 3 or 4 times at a grid point, the average noise levels does not alter anymore the value, the number of measurements is sufficient. If the average noise level alters more than 1 dB, then additional measurements are recommended.
The microphone should be placed at a distance of 1 m from the buildings façades exposed to the higher noise and at least 4 m from ground. In absence of buildings, the microphone should be placed in the position of sensitive receivers. The output data required for the measurement campaign is:
the sound pressure levels A-weighted, LAeq, measured in octave or even in 1/3 octave bands; the maximum sound pressure level weighting A and with time weighting Slow, LpASmax; the percentile levels, L90 – L95 – L99; the spectral analysis (if available) of 1/3 octave bands, also in order to detect the presence of tonal and impulsive components; the background level, to verify that the sound level measured in the current source is 10 dB higher than the background noise. If yes, the error due to the
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neglecting background noise is less than 5.0 dB. If not, measured sound levels has to be “cleanse” from the background noise by means of: (
)
where
Ls is sound level of the sound source; Lm is total measured sound level (sound source + background noise); Lb is measured background noise; i is referred to the ith frequency band
The values obtained should be compared with the maximum levels established as limit.
Analysis of most critical sources Once the monitoring activities have been conducted, it is necessary to identify the most critical of the sound sources. They can be identified through:
Sound pressure levels from the source Sound emission spectrum (if available) Sound emission day period The sound pressure level, depending on the source sound power, and the spectrum are features of the sound source. The higher is the sound pressure level and the more it is concentrated in the most sensitive human hearing frequencies range, the more the sound source will be critical. The sound emission day period is important because the noise produced by a given plant can be covered by the noise from other activities in the surrounding areas.
Reports The results of the measurements shall be recorded in a report which contains at least the following data: Date, place, time of detection and description of weather conditions, wind speed and direction; Reference, observation and measurement time;
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Complete measuring cycle, in particular focusing on the used equipment, its accuracy and calibration certificate; Noise levels detected; Results and conclusions; Names list of the observers/samplers who attended the measurement; Identification and signature of the acoustic competent technician who performed the measurements.
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Seawater supports a multitude of functional coastal ecosystems and facilitates the distribution, abundance and life of organisms. Coastal water quality is very important from the environmental, economic and societal point of view and is deeply influenced by the surrounding land use including the quantitative and qualitative exploitation of agricultural/industrial use and urbanization including port activities. These actions may reduce water quality by increase sedimentation rates, nutrients, metal traces and hydrocarbons. Ports facilities are highly concentrated industrial areas which contain a variety of activities including container terminals, shipyards and cargo facilities. Indeed, these activities may have a direct and indirect high impact on water quality and it is therefore necessary to assess the impact of port operations quality in receiving waters in and around ports areas. To this extent, long term water quality monitoring projects results to be very important and shall be designed to complement, and in some cases expand, existing monitoring programs for some marine organisms. These plans aim to gain information on the quality of receiving waters through a structured long term sampling actions by implementing the port activities in order to minimize impacts on receiving waters.
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The first step for the Water topic is the same of the previous cases, Air and Noise: in the investigation of the methodologies to be applied in the improvement of the port environment scenario several actions have to be firstly implemented:
The assessment of: - Storm water runoff - Ships discharges (bilge and ballast water) - Sewage - Oil spillage - Anti-fouling paints - Liquid bulk storage and transfer (loading/unloading activities) - Non-bulk chemical storage and handling - Leaching and run-off of contaminants in stormwater - Port services and facilities - General operations that can impact surrounding urban areas The determination of the water pollutants that mostly affect the environmental sustainability. The consideration of the chemical, physical and microbiological aspects of water pollution in the Port.
The second step foresees the collection of useful resources and data that can be helpful during the analysis and evaluation of the action to be implemented. Specifically, the information to be needed is:
Concerning the reduction of the negative impacts of port general operations such as sewage/ships discharges - Time and Frequency of arrival of ships to the port - Type of open air stored bulk material: fertilizer, other materials - Water Spraying operation to bulk storages - Cleaning of trucks and other equipment (cement, ready mix concrete,..) - Type of merchandise loaded in incoming ships
In order to ensure the proper execution of measures campaigns and monitoring activities, some information on the measurement methods, on the investigated parameters, on data collection and on the technical equipment to be used in the topic Water are required. A good approach in this area is, in fact, indispensable in
49
order to obtain valid results and, thus, to ensure the maximum accuracy in the subsequent intervention actions.
Definitions Nutrients: are minor constituents of the sea water, essential for marine phytoplankton growth and health. They include mainly inorganic nutrients such as ammonium, nitrate, nitrite, phosphate and silicate. Unit of measurement: Âľmole/l. Chlorophyll a: a particulate organic compound necessary for the primary productivity in the sea water. It is abundant in all plants. Unit of measurement: Âľg/l. Hydrocarbon: the measurement of any oil pollution in seawater. Unit of measurement: mg/l. Transparency: the measurement of water clarity-turbidity. Secci disk: a tool for transparency measurement.
Basic measurement equipment The instrument used for monitoring should be chosen to include all the needed measurements for the port monitoring. Principally the monitoring system should include: Spectrophotometer, measuring nutrients and chlorophyll a in the water Spectroflourometer, measuring chlorophyll a and hydrocarbon and chlorophyll a in the water. pH meter, measuring pH Oxygen meter, measuring dissolved oxygen.
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Technical standards and methodology of the measurements Measurement has to be distinguished between short and long term.
Short term measurements
Conductivity Temperature Salinity Turbidity pH Dissolved Oxygen
Long term measurements Determination of nutrient and chlorophyll a Analysis proceedings All nutrients, and hydrocarbon has to be measured according to Grasshof et al. (1999). Chlorophyll a has to be measured according to Elizabeth and Gary (1994). Generally nutrient analysis have to be made in duplicate. Absorption has to be measured in a 4 cm cell using a Pye Unicam. Sp6-550 UV\VIS spectrophotometer. Chlorophyll a has to be measured flourometically using a Turner designs TD-700 flourometer.
Determination of ammonia Reagents Citrate buffer: 120 g of trisodium citrate dihydrate and 20 ml of 0.5M NaOH to be dissolved in 500 ml of fresh deionized distilled water. Phenol-soduim nitroprusside: 19 g of phenol and 0.20 g of disodium nitropursside dihydrate to be dissolved in 500 ml of fresh deionized distilled water.
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Soduim hydroxide-hypochlorite: a solution containing 0.15 g chlorine in 100 ml of 0.5M NaOH has to be prepared by diluting 6ml of commercially vailable (2.5% chlorine) hyopchlorite to 100 ml with 0.5M NaOH. Stock standard solution of ammonia nitrogen (5000 M): 0.066 g of ammonium sulfate to be dissolved in 500 ml of fresh deionized distilled water.
Analysis proceedings 25 ml sample has to be transferred into a 50 ml screw cap test tube, followed by sequential addition of 1 ml of reagents 1, 2 and 3 using an Eppendorf pipette. The reaction mixture has to be well shaken after each addition. The tube has to be closed and kept in the dark at room temperature overnight. After a minimum of 16 hours, the absorption has to be measured in a 4 cm cell at 630 nm.
Determination of nitrate and nitrite Nitrate reduction cadmium column The known method is made for the reduction of nitrate (60) except that two modifications which are decreasing the column length to 10 cm instead of 30 cm and keeping the Cd granules untightly packed. These modifications have three major advantages: 1) save analysis time (elution of the samples takes only one minute instead of five in the old method), 2) decrease the sample size from 100 to 50 ml and 3) increase the reduction efficiency to exceed 98%. Reagents Buffered concentrated ammonium chloride: 100 g of ammonium chloride and 1 0ml of ammonium hydroxide to be dissolved in 500 ml of fresh deionized distilled water. Un buffered concentrated ammonium chloride: 50 g of ammonium chloride to be dissolved in 25 0ml of fresh deionized distilled water. Dilute ammonium chloride: 25 ml of reagent 2 to be diluted to 1000 ml using fresh deionized distilled water.
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Sulphanilamide: 5 g of sulphanilamide to bedissolved in 50 ml of concentrated HCl and 300 ml of fresh distilled water and made up to 500ml with fresh deionized distilled water. Naphthylethylenediamine dihydrochloride: 0.50 g of N-1naphthylethylenediamine dihydrochloride to be dissolved in 500 ml of fresh deionized distilled water. Nitrate stock standard solution (5000 M): 0.1002 g of potassium nitrate to be dissolved in 100ml of fresh deionized distilled water. Nitrite stock standard solution (5000 M): 0.0345 g of sodium nitrite to be dissolved in 100ml of fresh deionized distilled water. Reagents 4, 5 and 7 have to be used for both nitrate and nitrite, while the other reagents have to be used for nitrate determination only.
Nitrate analysis proceedings At every nitrate determination session, the nitrate reduction column has to be cleaned and efficiency has to be checked, by eluting the column with 100-150 ml of dilute ammonium chloride (reagent 3) followed by running blanks and standard. Efficiency of the column has to be maintained above 98%. For reducing the nitrate content of the sample to nitrite, 50 ml samples have to be transferred into Erlynmayer flasks followed by the addition of 2 ml of buffered concentrated ammonium chloride (reagent 1). The flasks has to be then well shaken and the content of each flask was eluted through the nitrate reduction column. Elution has to be carried out in the manner described in Strickland and Parsons (60). 25 ml of the eluted sample has to be collected in the original Erlynmayer flask, followed by the addition of 0.5 ml of sulfanilamide (reagent 4). The reaction mixture has to be shaken and after 2-3 minutes, 0.5 ml of naphthylethylenediamine dihydrochloride (reagent 5) has to be added. After 10 minutes the absorption of the sample has to be measured in a 4 cm cell at 540 nm. Suitable aged sea water has to be used as a blank for nitrate. Nitrite analysis proceedings 25 ml samples have to be transferred into 50 ml screw cap test tubes and treated in the same way as the reduced nitrate sample. Aged sea water has to be used as a blank.
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Determination of phosphate Reagents Diluted sulfuric acid (4.75M): 126.5 ml of concentrated sulfuric acid to be diluted to 500 ml with fresh deionized distilled water. Ammonium molybdate: 18 g of ammonium molybdate tetrahydrate to be dissolved in 200 ml of fresh deionized distilled water. The reagent to be stored at room temperature. Potassium antimony tartrate: 3.25 g of potassium antimony tartrate to be dissolved in 100 ml of fresh deionized distilled water. Ascorbic acid: 17.5 g of ascorbic acid to be dissolved in 250 ml of fresh deionized distilled water. The reagent has to be stored in a deep freezer. Mixed reagent: 100 ml of this reagent to be prepared by mixing 40 ml reagent 1 + 9.0 ml of reagent 2 + 1.0 ml of reagent 3 + 25 ml of reagent 4. This reagent has to be prepared fresh just before use. Stock standard solution (5000 M): 0.068 g of potassium dihydrogen phosphate to be dissolved in 100 ml of fresh deionized distilled water. Analysis proceedings 25 ml samples has to be transferred into screw cap test tubes, followed by the addition of 2 ml of mixed reagent (reagent 5). The tubes have to be then covered and well shaken. After 10 min the absorption has to be measured in a 4 cm cell at 885 nm. Aged sea water has to be used as a blank.
Determination of silicate Reagents Diluted sulfuric acid (2.65M): 71 ml of concentrated sulfuric acid to be diluted to 500 ml with fresh deionized distilled water. Ammonium molybdate: 35 g of ammonium molybdate tetrahydrate to be dissolved in 250 of deionized distilled water. The reagent has to be stored at room temperature. Oxalic acid: 11.25 g of oxalic acid to be dissolved in 250 ml of fresh deionized distilled water. The reagent has to be stored frozen. Ascorbic acid: 3.15 g of ascorbic acid to be dissolved in 250 ml of fresh deionized distilled water. The reagent has to be stored frozen.
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Molybdate reagent: 40 ml of this reagent to be prepared by mixing of 20 ml of reagent 1 and 20 ml of reagent 2. Prepared fresh just before use. Acid reagent: 50 ml of this reagent to be prepared by mixing 25 ml of reagent 3 and 25 ml of reagent 4. Prepared fresh just before use. Stock standard solution (5000 M): 0.094 g of sodium silico fluoride to be dissolved in 100 ml of fresh deionized distilled water.
Analysis proceedings 25 ml samples have to be transferred into screw cap polyethylene bottles, followed by the addition of 1 ml of molybdate reagent (reagent 5). The bottle has to be then closed and well shaken. After 8-10 min 2 ml of acid reagent (reagent 6) has to be added, and the bottle closed and well shaken. After 1-2 hours, the absorption has to be measured in a 4 cm cell at 810 nm. Deionized distilled water has to be used as a blank.
Determination of Chlorophyll a Apparatus and Equipment Fluorometer: Turner designs, td-700 equipped with high intensity blue lamp or daylight white lamp, red-sensitive photomultiplier, and filters for excitation (436nm) and emission (680nm). Centrifuge, capable of 675 g. Tissue grinder. Aluminum foil. Glass test tubes (13 mm) for the fluorometre. Cellulose membrane filter (0.45 um). Reagents Acetone (90%): 900 ml acetone to be diluted to 1000 ml with fresh deionized distilled water. Chlorophyll a stock standard solution: obtained from commercial supplier.
Analysis proceedings Chlorophyll a determination has to be carried out flourometrically as described by Elizabeth and Gary (62). One liter of sea water has to be filtered through a cellulose
55
membrane filter. The filter has to be then placed in a glass tube wrapped shield with aluminum foil. 10 ml of 90% acetone has to be added into the test tube. The membrane filter has to be ground using a tissue grinder and then kept in a refrigerator at 4°C over night. The mixture has to be then centrifuged for 5 minutes at 5000 rpm, and Chlorophyll a content has to be measured in a 13 mm glass test tube using the direct concentration calibration (sec. 2.4.2) method. 90% acetone has to be used as a blank.
Determination of Hydrocarbon Hydrocarbon has to be measured according to Grasshof et al. (1999). Analysis proceedings One liter of sea water samples has to be extracted with 25 ml n-hexane using a separatory funnel or other appropriate preparatory methods to obtain necessary quantitation limits. 25 ml of supernatant part has to be retrieved from separatory funnel. The analysis of the 25 ml sample has to be conducted with the spectroflourometer using 1 cm cell by applying a wavelength excitation of 310 nm and emission of 360 nm.
Reports The results of the measurements shall be recorded in a monthly report which contains following: Date, place, and time of detection; Reference, observation and measurement time; Results and conclusions.
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For further information please contact: Corrado Schenone University of Genoa – DIME Via all’Opera Pia 15/A - 16145 Genova (ITALY) Tel: +39 010 353 2577 Fax: +39 010 311870 e-mail: info@mesp.org
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