WASTEWATER FROM SHIPYARDS

NARCIZA TOPOR

Abstract. Oil lost and discharged represents a direct and significant pollution threat for marine life as well as industries, which depend on clean water and shore, notably tourism, fishing and aquaculture. Oil is used by the population at large and enters the marine and coastal environment not only direct, as in shipping, oil drilling etc. but also as final sink from a large variety of hinterland uses. The wastewater from shipyard operations like vessel cleaning, operations, solvent cleaning and degreasing operations including fugitive emissions will generate significant quantities thus making it imperative on part of environmental managers to minimize the resulting water pollution. For better management of wastewater, it is important to know the characteristics of wastewater Keywords: wastewater, wastewater stream, wastewater concentrations, specific pollutants, effluent quality, influent characteristics, treatment capacity, treatment efficiency.

1. Introduction The impact of the pollutant depends on type of oil, sensitivity of the area (e.g. salt marsh damage may be almost irreversible, while a rocky shore may be hosed down with relatively quick and satisfactory recovery), weather and how the pollution is tackled. This variability makes oil as state indicator prone to argument and highlights the need for controlling the handling of oil and avoiding loss or illegitimate disposal. The shipyard industry generates significant quantities of wastewater from various operations. Some of the major operations that generate wastewater are vessel cleaning operations, water used for cleaning the equipment, and water used in the processes. Efficient management of shipyard wastewater requires understanding of specific pollutants present and their concentrations. Integration of environmental plans minimizes duplication and encourages coordination between safety and health, emergency response, and environmental disciplines. Most of the management techniques like source reduction, waste minimization, control, treatment etc. can be effectively utilized once the composition of the

Department of Physics, The Ovidius University of Constana, Constana, 900, Romania.

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waste stream is known. This paper is the compilation of the knowledge acquired through the shipyard interaction. 2. International conventions and agreements Worldwide the MARPOL 73/78 Annex 1 Regulation for the Prevention of Pollution by Oil applies. This is concerned with vessels and harbours only. Other conventions and agreements cover specific areas and include land-based sources e.g. OSPARCOM for the North-East Atlantic, the Mediterranean Blue Plan, Odessa Declaration, Black Sea Action Plan. EU law: tries to control oil pollution in three ways: 1. by limiting the pollutant discharge such as Dangerous Substances Directive 76/464/EEC, Barcelona Convention concluded on behalf of the EU by Council Decision 77/585/EEC and approval of the oil pollution control protocol of 1/420/EEC; 2. by setting receiving water standards (eg. bathing water 76/160/EEC, shellfish water 79/923/EEC) and 3. Management, practise include emergency and information such as Directive 93/75/EEC on minimum requirements for vessels bound for or leaving EU ports and carrying dangerous or polluting goods, the North Sea decision 84/358/EEC approving the Bonn Agreement to ensure active cooperation between riparian states in case of pollution incidents and its equivalent for other seas. Decision 86/85/EEC sets up an information system on oil spills. A EU Directive on oil reception facilities is being prepared. 3. Wastewater characterization based on process knowledge and wastewater analysis Characterization forms basis for managing the shipyard wastewater and to improve the existing practices. In order to design onsite wastewater treatment systems, we must consider the nature of the wastewater because the effluent quality depends upon the influent characteristics. The treatment capacity and treatment efficiency of systems are calculated based upon the influent concentrations and the effluent requirements. Efficiency = [(C in Cout )/Cin ] 100 Where: Cin = Influent concentration (typically mg/l) Cout = Effluent concentration (typically mg/l) And Efficiency is expressed as a percentage (%)

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Also, the treatment capacity over time for biochemical processes is usually modelled as a first-order equation such that Ct/C0 = e kt Where: Ct = Concentration at time, t (typically in mg/l) C0 = Initial concentration at time = 0 (typically in mg/l) k = reaction rate constant (typically in days1) t = time (typically in days) By exercising the characterization process, the constituents of the wastewater stream and their concentrations are known. Wastewater characterization can be done by looking into the processes and also, by sampling. Process knowledge helps in estimating roughly various pollutants by analysis of the raw materials going into the process. Also, the evaluation of various operations can help in understanding the possible pollutants that are coming out of the operations. Sampling is done to know the exact composition of the wastewater stream and the concentrations. The various processes and/or operations that contribute to the wastewater have been given in the following sections.

3.1. Vessel Cleaning Operations The vessel cleaning operations cover many different areas and include those operations as tank washing operations, pipeline cleaning operations, mucking operations, chemical cleaning, chemical spot washing, engine room cleaning, and others. The wastes associated with the vessel cleaning are actually generated when the ship is in use. The most common wastes from the vessel cleaning operations are the bilge wastes, which are a mixture of oil and fuel with water. Therefore, the pollutants/parameters include oil & grease, COD (Chemical Oxygen Demand), phenols, purgeable halocarbons and TSS (Total Suspended Solids).

3.2. Pipeshop Operations The department of pipeshop in the shipyard is concerned with the testing of the pipes for leakages, cleaning of the pipes after installation and other related activities. The shop uses different types of solutions for cleaning the pipes which include some rust inhibitors. Some of the solutions include sodium hydroxide, sodium nitrite, sodium silicate, dry

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chlorine (granular), morpholine, hydrazine, potassium hydroxide, and others. The cleaning of the pipes is done to remove the rust and the scales formed inside the pipes. The rust and the scales contribute to the TSS component of the stream. Some of the cleaning solutions like sodium hydroxide, potassium hydroxide also affect the pH of the wastewater coming out of the operation.

3.3. Operators Department Other major source of wastewater from the shipyard is the operators department. The job of the operators is to run trial tests of the ship before handing over to the customer. The testing includes main engine testing, boiler testing, testing of cranes, refrigerators, automated controls etc. In the process of testing the ship, the department generates wastes like spent engine oil, cleansing solutions, spent lubricating oils and wash water. The pollutants/parameters include oil & grease, COD, phenols, purgeable halocarbons, and TSS. Solvent Cleaning and Degreasing Operations Degreasing operations also contribute to the wastewater generation in the shipyard. These operations are again sub-divided into other operations like wipe cleaning, soak cleaning, ultrasonic cleaning, diphase cleaning, steam gun stripping, vapor phase cleaning, mechanical cleaning, and others. The pollutants/parameters from these operations include oil & grease, COD, and purgeable halocarbons. Other contributors to the wastewater are processes like wet blasting (TSS being the pollutant), chemical stripping, and hydro blasting. There are other main streams of wastewater from the shipyard. They are sanitary wastewater and stormwater. The characteristics of sanitary wastewater are well known and need not be discussed in detail here. However, the stormwater characteristics may vary depending on the shops or operations located within the area of concern. The concentrations of pollutants from stormwater outfalls of a typical shipyard are given in Table 1. The above sections enumerate the different types of pollutants from the processes and/or operations in the shipyard. Sometimes, the wastewater streams include heavy metals as pollutants. Some processes generate liquid wastes, which require handling as either solid or hazardous waste. Great care has to be taken when heavy metals are present owing to their toxicity. Table 2 gives results of the analysis of pipe shop effluent. Though the concentrations may vary, Table 2 includes all the pollutants/parameters that may be encountered in the shipyard operations.

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Table 1

Stormwater characteristics of a typical shipyard PARAMETER Oil & Grease (O&G) Chemical Oxygen Demand (COD) Total Organic Carbon (TOC) Cadmium Chromium (MQL= 0.10) Copper (MQL= 0.10) Lead (MQL= 0.005) Tin (MQL= 0.02) Zinc Outfall 1 3.0 31.0 8.4 0.02 7.0 BQL 0.05 0.0 0.02 CONCENTRATION, mg/l Outfall 2 Outfall 3 7.0 2 74.0 14.3 0.04 0.0 BQL 0.16 1.0 0.04 30 7.7 0.06 1 BQL 0.06 0 0.02 Outfall 4 1 19 7.3 0.09 7 BQL BQL BQL BQL

MQL = Minimum Quantification Level - USEPA Region VI NPDES; BQL = Below MQL Table 2 Wastewater characteristics of a typical pipe shop Parameter Biochemical oxygen demand Total suspended solids Chemical oxygen demand Total organic carbon Cadmium Chromium Copper Lead Mercury Nickel Silver Tin Zinc Oil and grease Phenol Concentration, mg/l 1358 660 3720 1240 0.004 0.015 6.3 0.187 <0.002 0.44 0.004 BQL; MQL = 0.020 2.44 133 0.100

The concentration of each of the pollutants of the wastewater stream is known by running analysis of the samples collected from the sources. In case of shipyards, regulations play an important role in managing the waste streams. Permits are required to discharge the wastewater generated in the shipyard. These permits generally specify the methods by which the pollutant concentration can be known. The management practices adopted in the shipyard are according to the guiding regulations so that the shipyard can be in compliance. The permits

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issued by various agencies specify the discharge limits for various pollutants. Therefore, the control options and the treatment technologies adopted are in proportion to comply with the discharge limits outlined in the permits. 4. Treatment The treatment of the wastewater is generally carried out on-site owing to substantial quantities generated. Treatment of wastewater involves preliminary treatment, primary treatment followed by secondary treatment. The secondary treatment can be chosen from two alternatives: biological treatment and physico-chemical treatment. These treatment options have been discussed in the following sections.

4.1. Biological Treatment Biological water treatment methods for the removal of heavy metals and other inorganic contaminants have grown in popularity during the last decade. Low costs and minimal sludge generation have convinced many environmental managers in the shipyard industry to experiment with biological systems. The key to successful implementation of biological water treatment is process control: specifically biological process control. Suspended solids in a shipyard wastewater can be of two types: settleable and non settleable. The non settleable particles can be colloidal and dissolved particles, both organic and inorganic. The organic biodegradable fraction can be removed using conventional biological treatment processes, while the inorganic colloidal solids need some form of flocculation to become settleable. A biological treatment plant is using biomass to convert pollution into water. Biological treatment is primarily aimed to reduce dissolved materials. Based on the wastewater characteristics of a typical shipyard, the following treatment processes are deemed necessary to obtain concentrations below discharge limits: preliminary treatment, primary treatment, secondary biological process, secondary settling, effluent filtration, adsorption of non biodegradable organics, final effluent disinfection and sludge treatment. 4.1.1. Preliminary Treatment The objective of preliminary treatment is the removal of coarse solids and other large materials often found in raw wastewater. Removal of these materials

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is necessary to enhance the operation and maintenance of subsequent treatment units. Preliminary treatment operations typically, in a shipyard wastewater treatment plant, include coarse screening, grit removal. In shipyards grit would be composed of sand, metal chips, or other heavy discrete particles generated in metal surface preparation. In grit chambers, the velocity of the water through the chamber is maintained sufficiently high, or air is used, so as to prevent the settling of most organic solids. Grit removal is not included as a preliminary treatment step in most small wastewater treatment plants. Flow measurement devices, often standing-wave flumes, are always included at the preliminary treatment stage. 4.1.2. Primary Treatment The objective of primary treatment is the removal of settleable organic and inorganic solids by sedimentation, and the removal of materials that will float (scum) by skimming. Approximately 25 to 50% of the incoming biochemical oxygen demand (BOD5), 50 to 70% of the total suspended solids (SS), and 65% of the oil and grease are removed during primary treatment. Some organic nitrogen, organic phosphorus, and heavy metals associated with solids are also removed during primary sedimentation but colloidal and dissolved constituents are not affected. The effluent from primary sedimentation units is referred to as primary effluent. Wastewater from barge cleaning, bilge wastes, process waters and sanitary wastewater have concentrations of oil and grease typically between 100 and 150 mg/L. The general discharge limit for oil and grease is 15 mg/L. Hence, an oil-water separator is usually employed to separate out the oil from the wastewater. This separated oil can be sold to outside customers for use as fuel. 4.1.3. Secondary Treatment The objective of secondary treatment is the further treatment of the effluent from primary treatment to remove the residual organics and suspended solids. In most cases, secondary treatment follows primary treatment and involves the removal of biodegradable dissolved and colloidal organic matter using aerobic biological treatment processes. Aerobic biological treatment is performed in the presence of oxygen by aerobic microorganisms (principally bacteria) that metabolize the organic matter in the wastewater, thereby producing more microorganisms and inorganic end-products (principally CO2, NH3, and H2O). Several aerobic biological processes are used for secondary

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treatment differing primarily in the manner in which oxygen is supplied to the microorganisms and in the rate at which organisms metabolize the organic matter. Biodegradable organics contained in shipyard wastewater can be easily removed using any of the conventional biological treatment processes or their combination. Several of the available alternatives, namely, suspended growth processes (conventional activated sludge, extended aeration) and fixed-film processes (trickling filters, rotating biological contactors, aerobic fluidized beds) could be selected. High-rate biological processes are characterized by relatively small reactor volumes and high concentrations of microorganisms compared with low rate processes. Consequently, the growth rate of new organisms is much greater in high-rate systems because of the well controlled environment. The microorganisms must be separated from the treated wastewater by sedimentation to produce clarified secondary effluent. The sedimentation tanks used in secondary treatment, often referred to as secondary clarifiers, operate in the same basic manner as the primary clarifiers described previously. The biological solids removed during secondary sedimentation, called secondary or biological sludge, are normally combined with primary sludge for sludge processing. Common high-rate processes include the activated sludge processes, trickling filters or biofilters, oxidation ditches, and rotating biological contactors (RBC). A combination of two of these processes in series (e.g., biofilter followed by activated sludge) is sometimes used to treat municipal wastewater containing a high concentration of organic material from industrial sources. i The Activated Sludge Process In the activated sludge process, the dispersed-growth reactor is an aeration tank or basin containing a suspension of the wastewater and microorganisms, the mixed liquor. The contents of the aeration tank are mixed vigorously by aeration devices which also supply oxygen to the biological suspension. Aeration devices commonly used include submerged diffusers that release compressed air and mechanical surface aerators that introduce air by agitating the liquid surface. Hydraulic retention time in the aeration tanks usually ranges from 3 to 8 hours but can be higher with high BOD5 wastewaters. Following the aeration step, the microorganisms are separated from the liquid by sedimentation and the clarified liquid is secondary effluent. A portion of the biological sludge is recycled to the aeration basin to maintain a high mixed-liquor suspended solids (MLSS) level. The remainder is removed from the process and sent to sludge processing to maintain a relatively constant concentration of microorganisms in the system. Several variations of the basic activated sludge process, such as extended aeration and oxidation ditches, are in common use, but the principles are similar.

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The activated sludge process can be easily employed for treating shipyard wastewater as it does not occupy much space. The treatment process can be carried out in floating tanks placed on a barge. The complete mix system may require heating to enable proper temperature conditions for the microbes to work effectively. ii Trickling Filters A trickling filter or biofilter consists of a basin or tower filled with support media such as stones, plastic shapes, or wooden slats. Wastewater is applied intermittently, or sometimes continuously, over the media. Microorganisms become attached to the media and form a biological layer or fixed film. Organic matter in the wastewater diffuses into the film, where it is metabolized. Oxygen is normally supplied to the film by the natural flow of air either up or down through the media, depending on the relative temperatures of the wastewater and ambient air. Forced air can also be supplied by blowers but this is rarely necessary. The thickness of the biofilm increases as new organisms grow. Periodically, portions of the film 'slough off the media. The sloughed material is separated from the liquid in a secondary clarifier and discharged to sludge processing. Clarified liquid from the secondary clarifier is the secondary effluent and a portion is often recycled to the biofilter to improve hydraulic distribution of the wastewater over the filter. The TF process efficiently treats industrial wastes having a high percentage of soluble, small molecule organic material, and readily removes suspended and colloidal organics by the combined process of flocculation, adsorption, and enzyme complexing (WEF, 1991). The versatility of trickling filters towards variations in the wastewater characteristics makes them useful for treating shipyard wastewater as the wastewater from various operations varies with factors like different types of vessels being cleaned, different kinds of processes being employed at times owing to their intermittent nature, and others. Also, the ability of TFs to treat low-strength streams can be utilized for treating shipyard wastewater. iii Rotating Biological Contactors Rotating biological contactors (RBCs) are fixed-film reactors similar to biofilters in that organisms are attached to support media. In the case of the RBC, the support media are slowly rotating discs that are partially submerged in flowing wastewater in the reactor. Oxygen is supplied to the attached biofilm from the air when the film is out of the water and from the liquid when submerged, since oxygen is transferred to the wastewater by surface turbulence created by the discs' rotation. Sloughed pieces of biofilm are removed in the same manner described for biofilters.

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Tertiary and/or advanced wastewater treatment is employed when specific wastewater constituents which cannot be removed by secondary treatment must be removed. Individual treatment processes are necessary to remove nitrogen, phosphorus, additional suspended solids, refractory organics, heavy metals and dissolved solids. Because advanced treatment usually follows high-rate secondary treatment, it is sometimes referred to as tertiary treatment. However, advanced treatment processes are sometimes combined with primary or secondary treatment (e.g., chemical addition to primary clarifiers or aeration basins to remove phosphorus) or used in place of secondary treatment (e.g., overland flow treatment of primary effluent). As part of tertiary treatment, the treatment plant could have filtration to further remove suspended solids, and adsorption, to remove non biodegradable organic compounds that may be toxic to aquatic life. The filtration of effluents from wastewater treatment processes is a relatively recent practice (Metcalf & Eddy, 1991), used for achieving supplemental suspended solids removal from biological or chemical treatment processes. Carbon adsorption is an advanced wastewater treatment method used for the removal of refractory organic compounds as well as residual amounts of inorganic compounds such as nitrogen, sulfides, and heavy metals (Metcalf & Eddy, 1991). Filtration of effluents through granular activated carbon beds must be preceded by sand filtration to protect the carbon particles against significant pressure loss, channeling or blockages. If powdered activated carbon (PAC) is used, it is usually added to the activated sludge aeration basin, so that biological oxidation and physical adsorption occur simultaneously.

4.2. Physico-chemical Treatment The main difference between the biological treatment plant and physicochemical treatment is that the latter does not rely on bacteria to remove organic matter from wastewater. To remove colloidal particles, both organic and inorganic, chemical addition is required. Coagulants added to the wastewater stream will destabilize the colloidal suspensions and floc formation will take places in a flocculator. Dissolved organic substances must be removed by adsorption in activated carbon filters. Thus, the sequence of treatment units in a typical physico-chemical shipyard treatment plant would be the following: preliminary treatment, chemical addition, flocculation, dissolved air flotation, effluent filtration, adsorption of organics, final effluent disinfection and sludge treatment. This section will only describe the new units needed in physicochemical treatment, namely, flocculation and dissolved air flotation.

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4.2.1. Flocculation Flocculation is the agglomeration of destabilized particles into microfloc and after into bulky floccules which can be settled called floc. The addition of another reagent called flocculant or a flocculant aid may promote the formation of the floc. The factors, which can promote the coagulation-flocculation, are the velocity gradient, the time, and the pH. The time and the velocity gradient are important to increase the probability of the particles to come together. Moreover the pH is a prominent factor in the removal of colloids. The purpose of flocculation is to form settleable particles from the destabilized colloidal particles. The flocculator is a separate reactor, with a holding time of around 30 minutes, where the wastewater is agitated gently with paddles rotating at a velocity between 1.3 and 3.3 ft/s. This gentle agitation will promote particle growth so that the larger floc particles will be easily separated by gravity or by flotation. 4.2.2. Dissolved Air Floatation The addition of chemical coagulants (alum, polymers) will also destabilize emulsified oil particles and promote the formation of oil droplets; these larger particles can be easily dragged to the surface by the small air bubbles generated in the flotation unit. Dissolved Air Flotation (DAF) is a solids-liquid separation process that transfer solids to the liquid surface through attachment of fine air bubbles to solid particles. The phenomenon of DAF consists of three processes: bubble generation; attachment of solids to the bubbles, and solids separation. The DAF process involves holding recycled effluent for 0.3 to 3 minutes in a retention tank and introducing air at high pressure (60-90 psi). When the pressure is released as the recycle mixes with the feed stream in the flotation chamber it forms microbubbles (4-50 micors), removing a large number of small floc particles by adhesion of air bubbles on the floc surface, entrapment under the floc and absorption into the floc. The attraction between the air bubbles and particles is primarily a result of the particle surface charge and bubble size distribution. There are three modes of injecting air bubbles into the waste stream: recycling, total pressurization, and partial pressurization. Total pressurization is used in small installations, whereas in larger units, recycle or partial pressurization is usually selected (EPA 1973a, 1973b). With wastewater

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containing emulsified oil or grease, chemical conditioning is necessary to break the emulsion and form a floc to absorb the oil or grease. The particle growth preceding floatation contributes to the effectiveness of the floatation process. Therefore, when chemical addition is used to break up the emulsion, a flocculation chamber is generally used preceding the floatation process. In the case of shipyard wastewater, excluding storm water runoff, treatability studies should be conducted to determine not only the design parameters for the DAF unit, but also to determine whether chemical treatment and flocculation are needed to improve the DAF unit efficiency. 5. Conclusions Various shipyard operations like vessel cleaning, solvent cleaning and degreasing and others generate huge quantities of wastewater. The quantities from the process/washwaters in a typical shipyard can be as high as million tons in a year. Such high quantities invariably draw the attention of the shipyard environmental managers to reduce the waste streams. The first step towards reducing the pollution is the characterization which is done to differentiate various pollutants in the waste stream and their respective concentrations. Process-wise delineation of pollutants will help in better management of wastewater. Waste minimization methods with stress on source reduction can be employed to reduce the pollution. Various methods like process changes, replacement of solvent strippers, alternative cleaning solutions, cleaner abrasive media, efficient rinse systems, effective reuse and recycling options including evaporation, reverse osmosis, electrolysis, and others are viable source reduction methods. The biological treatment can employ either the activated sludge process or the trickling filter concept in the secondary treatment. On the other hand, physico-chemical treatment does not involve treatment by microorganisms but will require additional physical processes like flocculation and dissolved air floatation.

REFERENCES KURA, B., TADIMALLA, R., SAHA, S., Wastewater from Shipyards Characterization, Minimization, and Treatment. ECKENFELDER, W. W., 1980, Principles of Water Quality Management, CBI Publishing Company, Inc., Boston, Massachusetts.

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Environmental Protection Agency, 1973a, Pretreatment of Poultry Processing Wastes, Upgrading Existing Poultry-Processing Facilities to Reduce Pollution, EPA Technology Transfer Publication. Environmental Protection Agency, 1973b, In-Plant Modifications and Pretreatment, Upgrading Meat Packing Facilities to Reduce Pollution, EPA Technology Transfer Publication. Environmental Protection Agency, 1994a, Guide to Cleaner Technologies Alternatives to Chlorinated Solvents for Cleaning and Degreasing, EPA/625/R-93/016. Environmental Protection Agency, 1994b, Guide to Cleaner Technologies Metal Surface Treatment and Plating Operations, EPA/625/R-94/007. Environmental Protection Agency, 1994c, Guide to Cleaner Technologies Organic Coating Removal, EPA/625/R-93/015. KIELY, G., 1997, Environmental Engineering, McGraw Hill, London, England. KURA, B., 1996a, Integrated Environmental Management Plan First Year Interim Report, Gulf Coast Region Maritime Technology Center Project No. AMTC95-008A. CHANG, E. L., CALVERT, J. M., KOLOSKI, T., PRICE, R., RATNA, B, 1997, Separation of Oil from Bilge Water. I. Bilge Water Characteristics and the Interaction of Bilge Water with Chemically Modified Surfaces, Naval Research Lab Washington DC.