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Environ Monit Assess (2014) 186:4871–4879

DOI 10.1007/s10661-014-3744-3

Influence of water salinity on corrosion risk—the case
of the southern Baltic Sea coast
K. Zakowski & M. Narozny & M. Szocinski &
K. Darowicki

Received: 10 January 2014 / Accepted: 18 March 2014 / Published online: 3 April 2014
# The Author(s) 2014. This article is published with open access at Springerlink.com

Abstract Water corrosivity in Gdansk Bay, Poland, the Introduction
southern part of the Baltic Sea, was investigated. The
analysed region is heavily industrialized, and the coast- From a chemical standpoint, seawater is an aqueous
line is very diverse. Twenty-seven test points along the solution of salts. On average, ocean water salinity equals
coastline were selected. Water parameters such as salin- approximately 3.5 % (Williams et al. 2010). Salinity is
ity, total dissolved solids content, resistivity, conductiv- evaluated by determination of [Cl−] ion concentrations
ity, oxygenation, pH and corrosion rate were deter- in water. Empirical dependence, which states that salin-
mined. The results of the investigation are presented. ity equals 1.80655 × [Cl−], is used. In practice, conduc-
Water samples were collected, and structural steel spec- tivity measurements are performed. Conductivity is con-
imens were exposed in the water for 2 months. The verted into salinity by employing empirical relation-
corrosion rate for each test point was determined and ships. A variety of salts compose ocean water, and their
plotted on a map. The spatial distribution of water typical quantity is reflected in artificial ocean water. The
parameters was calculated using the ‘inverse distance composition of artificial ocean water according to the
to a power’ method and presented on the maps. Salinity ASTM D1141-98(2013) ‘Standard Practice for the
did not exceed 0.7 %, and average corrosion rate Preparation of Substitute Ocean Water’ is presented in
equalled 0.0585 mm/year. Table 1.
Differences in local salinity might be a result of the
phenomenon of water evaporation, which increases sa-
Keywords The Baltic Sea . Seawater . Corrosion rate . linity levels (Da-Allada et al. 2013). A limited water
Water corrosivity . Salinity exchange in a given sea area and an uncompensated
sweet water inflow result in a decrease in salinity
(Zhang and Yan 2012; Rodhe and Winsor 2002). In
comparison to most oceanic waters, the Baltic Sea ex-
hibits low evaporation rates. The Baltic Sea is a margin-
K. Zakowski : M. Narozny (*) : M. Szocinski : al sea, and water exchange with the Atlantic Ocean is
K. Darowicki
Department of Electrochemistry, Corrosion and Materials
only possible through the narrow Danish straits. For
Engineering, Chemical Faculty, Gdansk University of these reasons, the Baltic Sea is considered to be a
Technology, moderately salinized sea—approximately 1 % (Feistel
11/12 Narutowicza St, 80-233 Gdansk, Poland et al. 2010). The salinity of Gdansk Bay is even lower—
e-mail: micnaroz@student.pg.gda.pl
approximately 0.7–0.8 %—due to a high sweet water
M. Narozny inflow, mainly from the Vistula River mouth near the
e-mail: narogu@wp.pl Isle of Sobieszewo (Rak and Wieczorek 2012).

0000000136 Neville and Morizot 2002.695 0. which occur close to the water surface. natural water increases proportionally with salinity. This phenomenon is caused by the fact Material and methods that corrosion rates tend to increase when water conduc- tivity increases. Within the range of the pH observed in MgCl2 5.2 0. plete protection. ASTM D1141-98(2013) 2012).0322 from the corrosion risk standpoint are oxygen and car- KCl 0. the southern part of the Baltic seawater (Melchers 2006. Gdanskie Zakłady Nawozow Fosforowych Fosfory Sp. Rose et al. Pb(NO3)2 0. above 3 % measurements of typical parameters of water were per- salinity. 2013) and ca. Water samples were collected in order to . and it NaF 0. 2012. 2007). z o.00280 ity. Thus. the lower the In selected places at the Gdansk Bay coastline.00000276 gen is influenced not only by temperature.000749 ter more acidic (Rerolle et al. LOTOS S. Jia-Yuan et al. This part of the Polish coastline is greatly diversi- rosion protection systems mostly consist of mutually fied.000000183 2003). the corrosion rate in seawater decreases.681 Oatts 1984). 2011. Protection technology should be adjust.201 0. 2009) but Cu(NO3)2 0.0000308 0. atmospheric Mn(NO2)2 0. resistivity. photosynthesis Zn(NO3)2 0.000000944 pressure and water salinity (Debelius et al.144 seawater.16 0.00558 ide decreases with an increase in temperature and salin- KBr 0. Corrosivity of heavily influences the integrity of these facilities. water corrosivity decreases (Kirk and Pikul 1990). Siarkopol Gdansk (sulphur exporter). 2013).00000049 0. The corrosivity of water number of mutually dependent factors. Ayers 1991). If salinity exceeds 3 %. oil storage-handling bases. Sea. bridges and and to present the typical water parameters (oxygena- other stationary offshore structures are being built. The. piers. salinity) of se facilities are susceptible to the corrosive influence of Gdansk Bay coastal areas.4872 Environ Monit Assess (2014) 186:4871–4879 Table 1 Artificial ocean water composition according to the pH of oceanic water ranges from 7. Liu et al. 2013). For instance.027 0. 2012. oil refinery (Poland’s second greatest pet- ed to the local degree of corrosion risk caused by the rochemical plant). the corrosion rate is approximately equal. Their anticor.53 0.114 Gases dissolve in water and the most important ones CaCl2 1.003 0.000000855 also by biological activity.000034 0.0000994 0. tion.0000066 0. Wong and NaCl 24. of the Isle of Sobieszewo.1 (Rerolle et al.000000266 processes. The amount of dissolved oxy- Ba(NO3)2 0. A properly designed corrosion protec.o. Hajeeh 2003). there is a major infrastructure development affect corrosion rates (Khana et al. many smaller maritime companies. Salt concentration [g/dm3] Salt [%] for example. Carbon dioxide influences water pH—it makes wa- H3BO3 0. Oxy- SrCl2 0. Na2SO4 4. Goldberg 1988). There is a great sweet and contaminated water supplementary coating (Hou Jian et al.0193 bon dioxide.000694 gen acts as a depolarizer in the cathodic half-cell. The aims of this paper are to evaluate corrosion risk harbours. water Due to the global economic and merchandise trade contamination (Melchers 2009. inflow from the Vistula River mouth in the proximity thodic protection systems (Hartt 2012.0000096 0. deposition of corrosion products (Hu Jiayuan et al. The formed.0000833 enhances corrosion risk. The higher the salinity is.101 0. field oxygen solubility is (Weiss 1970).A. harbour and shipyard and Gdynia and Gdansk Port The corrosion rate in seawater is a function of a large (Altayaran and Madany 1992).025 0. (phosphoric fertilizer producer). 2007) and fouling also expansion. total dissolved solids (TDS). a Polish Navy tion system should assure complete corrosion resistance.09 0. Lower-pH regions are situated near river mouths. The solubility of oxygen and carbon diox- NaHCO3 0. Higher-pH regions are where water blooms and tide pools are (Kharchenko et al. seawater environment (Al-Malahy and Hodgkiess 2003. Calcareous deposits (Zakowski et al. AgNO3 0. in- crease oxygen concentrations (Ayers 1991. The investigated area is The better the coating barrier properties are. 2013. in Polish coastal areas. the lower is heavily industrialized. There are two large shipyards in the cathodic current density required to guarantee com.9 to 8. Gdynia and Gdansk. Zakowski 2011). 2013. Zamanzade et al. New facilities such as ports.

The lower the temper. of S235JR structural steel. brackish (1. The locations where the measure. oxygen reduction reaction.000). The samples were exposed in indi- flow. Mn 1. to the Port of Gdynia. 1.04 max. Investigated water parameters Salinity mainly influences water resistivity. but their effect & pH on yearly averaged corrosion rate is not very significant.4 max. 2012. They can take place at a greater distance from the metal- were located along the Gdansk Bay coastline. N 0. At each and Sasidhar and Vijay Kumar 2008). For instance. Coupons 100×50 mm The corrosion rate in seawater is controlled by an were made of a S235JR 2-mm-thick carbon steel sheet. In the case of immersed structures. Thus. The coupons were made to the structure’s surface (Al-Fozan and Malik 2008). as compared to the electrolytes of higher Vistula River mouth near the Isle of Sobieszewo (Gdansk) electric resistivity. the electrodes tivity and higher electrolyte resistivity (Sharqawy 2013. from the metal contact.Environ Monit Assess (2014) 186:4871–4879 4873 perform laboratory exposure of corrosion coupons and increased oxygenation and enhanced oxygen migration determine their corrosion rates. salinity and electric conductivity/resistivity were 2010). dissolved salts. localization and water parameters states (Boerlage 2012). Water can be regarded as fresh for each and every point are presented in Table 2. It can be assumed that S 0. the galvanic corrosion process Twenty-seven measurement points were chosen. (TDS<1. range. 1997). The description. of which were made of AISI 316 steel.55 max.500 ppm). are unfavourable At every test point (Fig.012 max and Cu 0. measured with the conductivity meter. approximately 5 m away from the coastline. gen. which causes seawater to exhibit lower conduc. higher corrosion rates are observed in splash vidual containers to unstirred water at room temperature zones and in the locations where waving is greater due to (three coupons for every test point). The TDS parameter quantifies both organic and in- ments and the water samples were taken are presented in organic compounds in the ionic. It consisted of three probes. pH (activity of H3O+ ions) is important when a corrosion Gravimetric measurements were performed in order to protection system is designed due to its effect on the determine corrosion rates of steel coupons immersed in thermodynamic stability of water. in low-electric- resistivity electrolytes.500<TDS<5. P 0. Ten measurements were taken for 5 min at 30-s atmospheric corrosion rate due to its limited variation intervals. the lower the electrolyte electric resistance is. Performed tests do not take variable hydrodynamic & Temperature [°C] conditions such as storms and swells into account. They & Atmospheric pressure [hPa] increase the instantaneous corrosion rate. the maximum salt sol. The oxygen inflow to the The coupons were grounded to the Sa1 steel surface cathode is a function of oxygen concentrations and water preparation grade.04 max. The type of corrosion attack also Field measurement locations depends on resistivity. every measurement point. The composition of the Electrolyte conductivity increases with the tempera- S235JR steel is C 0. the pressure varies depending on the depth. the following seawater for passive metals and may cause local passive layer parameters were measured: failures initiating pitting corrosion (Ylasaari et al. the greater the corrosion rate may be. water sampled at every test point.000) or saline (TDS>5. & Dissolved oxygen content [mg/dm3] Sprouting and microbial activity were not investigated. a galvanic Ag/Zn probe was used. ture due to enhanced ion mobility. and the pressure factor is Corrosion rate determination more significant—it might cause corrosion cracking. Data logging was executed after 5 min of probe immer- Atmospheric pressure has almost no influence on sion. especially Cl−. Further- more. A Hanna & Salinity [‰] HI 9828 meter was used. particle or colloidal Fig. & Water resistivity [Ω cm]/water conductivity [μS/cm] Field measurements presented in this article were & TDS content [ppm] carried out in May 2013 and lasted 2 days. the lower the corrosion rate is. the probes were immersed ature is.2 max. 1). the greater the oxygen solubility in water is and 0. The TDS con- ubility also decreases (Helber et al. tent. Bingham et al. In order to investigate the concentration of dissolved oxy- As the temperature decreases.5 m deep. The exposure lasted .

name (Table 2. Instead of a distance between the measurement point and where Δmis the averaged coupon weight loss [g]. Mass loss measurements were per. latitude. been proposed. influenced by smaller watercourses and rivers. On the OX and OY axes. the salinity is sented values are the average of ten measurements taken approximately the same. Pre. stance in Jelitkowo (Table 2. TDS. the longitude and the latitude are presented in the NAD83 system. The ‘inverse distance to a power’ meth- Corrosion rate was determined using the following od is slightly different from the ‘inverse distance’ method. Local salinity is also A set of parameters—longitude. latitude). the samples were washed under running at 30-s intervals. power’ method. The Vistula River is a sweet water source for the Isle of Sobieszewo area. S is the grid node.0001-g accuracy. The further away from the Vistula River mouth one moves. order to obtain the linear corrosion rate expressed in The distribution of water salinity in the investigated the generally accepted unit [mm/year]. longitude. . region is presented in Fig. Vcorr was divided by sample density in cance of the points closer to the calculated grid node is. for instance in Gdynia (Table 2. The samples were washed. temperature. a power of that distance is calculated. location) and their exact locations are chloric acid mixed with 9 g/dm3 hexamethylenetetramine given in the North American Datum 1983 (NAD83) (CH2)6 N4 corrosion inhibitor. The the total coupon surface area [cm2] and t is the exposure greater the power coefficient is. system (Table 2. The test points described by their local water. Corrosion products were removed in 10 % hydro. resistivity. the greater the signifi- time [years]. and isolines representing water parame- formed with 0.4874 Environ Monit Assess (2014) 186:4871–4879 Fig. Δm relationship: vcorr ¼ S⋅t . ters have been calculated using the ‘inverse distance to a eraged mass loss of the three exposed coupons was used. Then. In the areas corrosion rate and pH—are presented in Table 2. for in- oxygenation. conductivity. an av. sample no. The maps have dried and weighted. For calculations. 2. 15). the higher the Results and discussion salinity is. located further away from watercourses. 1 Test points along the Gdansk Bay coastline 2 months. salinity. respectively.

0560 8.670 0.448051 6.17 10.370509 7.50 4.778285 54.65 9.0551 8.83601 54.480914 6.348152 7.756 6.73 10.0517 8.532 87.519107 6.802 4.28 9.67624 54.99 11.512 87.65 4875 .826569 54.620 6.66 8 Gorki Zachodnie—marina 18.0834 8.68 11.67 11.0419 8.570 0.27 11.844 6.780 0.454697 7.0802 8.00 5.589022 54.15 8.15 9.280 89.910 0.360 0.02 10.47 9.493 0.67 4.46 5 The Dead Vistula 18.423 95.551197 54.96 11.0546 8.406 0.355381 7.04 6.0398 8.559007 54.50 3.345051 13.42 7.60 10.56511 54.479719 6.456 87.00 4.43 9.659 6.970 6.17 8.430 0.573224 54.83 11.11 11.559039 54.604 131.852 6.25 5.00 5.32 8.0510 8.442 0.354562 9.83 5.0393 8.910769 54.769835 54.48 11.31 7.731579 54.0630 8.76 10.367571 8.36 2 The Isle of Sobieszewo 18.540 0.80 17 Sopot 18.00 5.574 0.108.99 8.99 26 Pomorski Harbour Basin 18.188 89.668 103.870 5.411132 8.45 10 Westerplatte 18.48 9.698 115.77 8.594 6.787 5.00 5.408266 7.834 5.0403 8.346101 7.550 0.86 10.94 River—pontoon bridge Environ Monit Assess (2014) 186:4871–4879 6 The Bold Vistula River 18.375521 7.0511 8.00 5.33 4.393652 8.603671 54.0540 8.43 11.64714 54.65 9 Stogi 18.05 10.65 16 Sopot Hestia 18.763 5.17 5.57 11.91 8.652 0.727 6.00 4.38 8.00 5.746 102.502433 6.688 86.425278 8.1061 8.873 5.403882 7.282 4.54 9.65 8.524 87.0550 8.0804 8.63 9.77 8.768 0.55 11 Martwa Wisła 18.438477 8.569 132.517868 7.579959 54.242 89.78 22 Gdynia Orłowo—pier 18.213 89.0540 8.566947 54.76 9.530 0.607 6.574 1.50 9.207 98.96 9.650 0.34345 10.20 5.698 85.785 4.762 85.577108 54.588 6.487 0.349 4.211 5.103 5.431869 8.0376 7.203 0.550381 54.640 6.Table 2 Set of values of measured parameters along the Gdansk Bay coastline Sample Location Longitude Latitude Temperature Oxygenation Conductivity Resistivity TDS Salinity Corrosion rate pH number [C] [g/mg/dm3] [μS/cm] [Ω cm] [ppm] [‰] [mm/year] 1 The Vistula River dug-through 18.68 9.85 24 Beniowski Quay 18.0404 8.632897 54.220 0.519911 5.534 0.939694 54.00 5.63 13 Brzezno 18.177 89.0610 8.423337 10.99 11.685016 54.547837 54.436 0.45 3 The Isle of Sobieszewo 18.564 117.00 5.94 23 Gdynia Coastwalk 18.740 6.452 87.71 19 Sopot—marina 18.23 10.71 237 0.318 88.80 18 Sopot—pier 18.600099 54.83 15 Jelitkowo 18.33 4 The Isle of Sobieszewo 18.13 11.98 9.390 0.28 9.87 21 Gdynia Orłowo 18.00 5.446837 5.940 84.74 474 2.50 14 Jelitkowo 18.740 103.726 6.0590 8.20 5.00 5.390 0.20 5.81 10.766 6.70 11.534243 4.66 25 President Harbour Basin 18.0415 8.0590 9.85 27 French Quay 18.850 6.17 3.00 4.872 0.64 10.0827 8.392 0.783295 54.24 11.0827 8.33 5.25 10.00 5.88 12 Nowy Port 18.230 0.565274 54.24 11.97 7 Gorki Zachodnie 18.0578 8.96 20 Sopot Kamienny Potok 18.480 87.875186 54.91 11.790 0.

The highest corrosion rate among investigated sam- ment was taken inside the bay.74 mg/dm3 and was observed at the Vistula sample nos. Yet.5 mm/ for both measurements. where the water is rather ples was recorded for the Vistula River dug-through unstirred and there is a small polluted river nearby. sample no. offshore structures. water resistivity.0 mm/year (Gardiner and The pH of seawater in Gdansk Bay is presented in Melchers 2003). (Table 2.78. 5 Map of seawater pH distribution along the Gdansk Bay Fig. 21–27). Thus. The Vistula River dug-through is River mouth. which were equal to approximately 0. The lowest oxygenation value was Fig. and resistivity is presented in ranged from 0. was slightly higher and was equal to 9.1061 mm/year. was the highest. 4 Map of resistivity distribution along the Gdansk Bay coastline Fig. and their values Fig. It has to be noted that locally where 11).035 to 0. 6. The determined corrosion rates for all test points line is presented in Fig.85). 4. The obtained corrosion rates are ity (Pearson correlation coefficient=−0. 5. the pH corrosion rate might rise significantly. In Gdynia Orlowo (test point 21). and the salin- The oxygenation of seawater in the investigated area is presented in Fig. imity of the river mouth. The measure. the low salinity of seawater has a Fig. string and oxygenation are high and the equal to 7. In the Dead Vistula River (Table 2.4876 Environ Monit Assess (2014) 186:4871–4879 Fig. year and in extreme cases 1. 7. 3 Map of TDS distribution along the Gdansk Bay coastline coastline . chemical plant sewage and fertilizer ‘Program rozwoju infrastruktury transportu wodnego run-off might be the causes of the very low water srodladowego w Polsce’—‘Program of inland water oxygenation (Environment and United Nations transport infrastructure development in Poland’. The distribution of TDS along the Gdansk Bay coast. sample no. are presented in Fig. The Vistula River is notoriously reported going to be greatly developed in upcoming years as a to be polluted at its river mouth.88.061 mm/ which might enhance biological activity leading to an year. obviously due to the prox- increase in the pH of the water. 3. 2 Map of salinity distribution along the Gdansk Bay coastline equal to 6. Environment Programme Global 2007). Only at two test points was water pH out of the 8– positive effect from the standpoint of corrosion risk of 9 range.5 % for such a strong correlation is the use of the same probe seawater. Bacterial pollution from part of the Polish Ministry of Infrastructure programme municipal sewage. the water was slightly more acidic and the pH was the water flows. The reason lower than typical corrosion rates for oxygenated 3. The TDS content is well correlated with resistiv. 1) and was equal to 1.

Apart from the Vistula River dug- through. it also had the lowest resistivity. The corrosion rates determined for the Gdynia Gdansk Bay coastline and Sopot areas vary between 0. The further away from the Vistula River mouth (Wall and Wadsö 2013). coastal area are in accordance with Wall and Wadsö the other factors must have had an effect on corrosion results for the steel sheet pile walls in the harbour of aggressiveness in that area.05 and 0. 7 Map of relative corrosion rates along the Gdansk Bay coastline . A low discrepancy of the measurements might occur due ity was the lowest.Environ Monit Assess (2014) 186:4871–4879 4877 one goes. Thus.06 mm/year study. to the presence of fewer and smaller watercourses. which was not investigated in this corrosion rates varied between 0. One can assume that it was a Halmstad on the Swedish west coast where average water pollution factor. The variation of results might be caused by the presence of the Vistula River arms and Fig.06 mm/year. 11) was the least corrosive. probably due to the mixing of seawater with sweet water from the river. the lower the corrosion rates are. sample no. 6 Map of seawater oxygenation distribution along the mouth. one would expect the opposite effect—lower The corrosion rates determined for the Gdansk Bay corrosion rates as compared to the other test points. If only those parameters were con.02 and 0. cerned. Wall and Wadsö determined Fig. The corrosion rate determined for water sampled from the Dead Vistula River (Table 2. In general. the corrosion rates obtained for the Gdansk area are more varied than the rates for the Gdynia/Sopot area.

E. (2012). water studies. of the seawater corrosion behaviour of a range of materials. T. history and current status. G. I. Open Access This article is distributed under the terms of the Creative Commons Attribution License which permits any use. 435–441. & Corrosion aggressiveness of seawater not only is a Gardiner. Another issue is the current condition of already Desalination. 6. M. according to EUROCODE 3. high attack’ and 0. A. and reproduction in any medium. inal author(s) and the source are credited. the corrosion aggressiveness of sensitivity analysis. Hartt. A. 509–518. R. & Forja. J. Atmospheric acidification in the Asian region. W. ISBN 92- steel was equal to approximately 0. (2012).. (2003). et al. 29(7). Adequate precautions should be taken when below the ocean mixed layer. & Offshore structures require corrosion protection sys. R. 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Hydrobiologia. part I: operational parameters influencing cor- influenced by other mutually supplementary factors rosion rates. the distance from Materials and Design. Environmental Monitoring and Assessment..08 mm/year corresponds to ‘seawater in the zone of Al-Fozan. provided the orig- ring the results to the initial steel sheet pile thickness. 250. P. 11(3). 68(12). s. B. those factors are Hajeeh. United Nations Environment Programme Global. (2003). 118(1). (2010). J. (2012). S. area indicate that in low-salinity seas. Y. (2008). W. 158(1–3). 2013. E.l. Comparative studies in the zone of permanent immersion’. Bingham. C. 6(1). An anticorrosion Research: Oceans. H. periodical control of the Environmental Monitoring and Assessment. 157–165. (1988).1 at the river mouth. 26. offshore infrastructure development in Poland between Ayers. Ocean Science. This fact has to be taken into ac- count when a new infrastructure is designed. the corrosion rate of 0.. Desalination. 225– infrastructure condition is recommended. 42(1–3). Anticorrosion performance of epoxy coat- system should involve proper selection of materials ings containing small amount of inherently conducting as well as application of adequate paint systems PEDOT/PSS on hull steel in seawater. Information needs for marine pollution such as temperature. R. (1991). A. Gomez-Parra. Seasonal mixed-layer salinity balance in the tropical Atlantic Ocean: mean state and seasonal cycle. 61–67. oxygenation.4878 Environ Monit Assess (2014) 186:4871–4879 corrosion rates by steel sheet pile thickness measure. Journal of Geophysical the construction is being designed. Burlington : United Nations water increases and the corrosion rate of structural Environment Programme Global Environment. References stance. 19(1–3).. Science and Technology.. (1992). Density and absolute salinity of the Baltic Gdansk Bay and approximately 0. Environment. S. & Hodgkiess. There was a rapid ter. 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