ASSESSMENT OF SEDIMENT CONTAMINANTS FROM CERAMIC PRODUCTION, A CASE STUDY OF FARSTAVIKEN Ola Öberg (Royal Institute of Technology, Stockholm, Sweden) ABSTRACT: A factory producing ceramics has discharged wastewater into a semi-enclosed water basin situated within the Stockholm archipelago. The objective of this study was to compare the discharge to the content of additional material at the bottom of the recipient. A material balance was made for dry substance, zinc, lead and cadmium. The discharge was estimated from interpolation of production figures between start year and 1968 when the discharge stopped. The additional material in the recipient was estimated as the integrated difference of yearly sedimentation rate between affected sedimentation beds and background values. The factory disposal up to 1968 was estimated to 18 000 tons of dry substance with a content of Zn and Pb of 40 and 50 tons respectively. The sediments show an additional content of dry substance of 14 000 tons, Zn 30 tons, Pb 25 tons and Cd 500 kg. Concentration intervals were for Zn 150 – 2 500 mg/kg for Pb 50 – 2 000 mg/kg and for Cd 2 – 60 mg/kg . It can be concluded that a material balance gives the order of magnitude and distribution of disposed material including contaminant components, even for a historical discharge. INTRODUCTION Farstaviken, a semi-enclosed fjord like basin situated within the Stockholm archipelago, has been a wastewater recipient for a factory engaged in ceramic production and for surrounding municipal wastewater discharges. Farstaviken is situated 20 km east of Stockholm. FIGURE 1. Stockholm Archipelago 1 Farstaviken is connected to a larger basin, Baggensfjärden through a straight with a depth of 6 meters, which reduces an effective water exchange of particularly bottom water. The surface area of Farstaviken inside the straight is 0,59 km2. Salinity of the water is 4-6 ‰ ( Lännergren, C., Johansson, P. 1997). There is no tidal activity in the area but meteorologically induced water level fluctuations, which together with the wind are the main driving forces for exchanging water (Engqvist, A. 1999). Depth profile Third deep area "Baggen A" Second deep area "Farsta C" First deep area "Farsta AB" Inner shallow area Outlet for waste disposal Farstaviken Baggensfjärden FIGURE 2. The depth profile of Farstaviken and of the closest part of Baggensfjärden. Factory waste disposal outlet and area cods. The ceramic production had two main production lines, the first making chinaware like plates and teacups, the other making sanitary ceramics like toilet seats. The production of chinaware started 1825 and stopped in 1990 (Arvidsson, et al. 1997). The production of sanitary ceramics started on a large scale after the Second World War when the construction of houses increased. This production is still going on. The origins of the wastewater discharged into Farstaviken was mainly from washing moulds and factory floors. The installation and use of water closets in the municipality began about 1950 and the discharges were disposed untreated to Farstaviken. All discharges stopped in 1968 when both the factory and the municipality built wastewater treatment plants. The main ingredients of ceramics are different kind of clays, in sanitary production kaolin, quarts and feldspar. To create a watertight surface the product are glazed. The glaze cover has often the same mixture as the product body but with an addition of something that reduces the melting temperature, a glazing agent. In the production of sanitary ceramics the glazing agent was zinc oxide, with a zinc content of 80% and 2 in the production of chinaware lead oxide with a lead content of 90%. Different metal oxides were used to create colours for decoration. Earlier studies of the sediments in the basin show elevated concentrations of lead, zinc and cadmium. The highest concentrations were found close to the discharge outlet in the inner shallow part of the bay (VIAK. 1984). Windgenerated waves and currents erode these sediments and they may be displaced to the accumulation areas in the basin. The municipal wastewater discharges consumed more oxygen than was mixed in by the wind and an anaerobic condition was permanently established in the bottom water. The sediment in deep bottoms that has the strongest anaerobic conditions also contains methane gas. This could clearly be seen on side-scan sonar images. (Anonymous. 1998a) Objective. The objective of this study was to compare the discharge from the factory to the content of additional dry substance, zinc, lead and cadmium at the bottom of the recipient. The objective was also to investigate possible resuspension and displacement of disposed material from the inner shallow part of the bay to deeper accumulation bottoms after 1968. The study will contribute to the basis for choice of remediation strategy. METHOD The study approach was to analyse how the disposed material is distributed in the different parts of the basin by use of a material balance. The factory discharge was estimated from production figures and the accumulation beds in the basin were investigated in a gradient from the factory. Factory Discharge. 1997 the production in the factory was 9 700 tons of sanitary ceramics. In the same year the wastewater treatment plant of the factory trapped 960 tons sludge, that is about 10% of the raw material used. Samples from the treatment plant show 4 700 mg/kg zinc in the dry waste (Anonymous. 1998b). It is possible to estimate the minimum amount of material that was discharged into the basin by assuming that the efficiency of using raw material was not higher during the period in which the wastewater was discharged directly into the basin. In the 1960´s glazing agents represented 5 % of the glaze cover, which on an average represented 10% of the weight of the manufactured product (Öberg. 2001). This is in agreement with the samples from the treatment plant. Inner Shallow Area. The area close to the factory was examined by core sampling from ice-cover during winter. The aim of this investigation was to compare concentrations found 15 (VIAK. 1984) and 25 (Orrje.1976) years ago in this area. 3 If the concentrations had changed, this can be due to displacement of the pollutants. The core sampling plastic-tubes had a diameter of 50 mm. They were pressed down 2 meters below sediment surface. The upper 30 cm of the cores was mixed separately. Five cores were analysed. A known volume and weight of about 100 grams of the sediment where boiled 1 minute with 100 ml 2M HCL. After depositing, 40 ml FIGURE 3. Inner shallow area with was used for analysing sampling points from 1976, 1984 with ICP equipment and 1999 (Inductively Coupled Plasma). The sediments were dried and weighed to achieve the dry weight. An estimated amount of Pb, Zn and Cd was calculated from the average of the five samples. Similar techniques were used in the 1976 and 1984 studies. Deep Bottom. The deeper bottom was investigated to find out how far the pollutant had spread from the source and how the deposition have changed historically in the accumulation bottoms. Farstaviken and the neighbouring basin Baggensfjärden were investigated. (Anonymous. 1998a). First the bottom was mapped with Side-Scan Sonar technique for detecting soft accumulation bottoms. A map showing the area of the soft bottoms was drawn and core samples were taken in sediment accumulation areas. The sampler used was a "Gemeni-sampler" which consists of two parallel metal tubes that are loaded with plastic tubes. The result is a double sample of two parallel cores with diameters of 8 cm and length of 80 cm taken at a distance of 25 cm from each other. One of the two cores was cut in two halves by length and photographed, the yearly sedimentation showed up as coloured layers in black, grey and olive green. The cores could be dated at all depth with help of the computer programs Photoshop and AutoCAD. The other core was analysed at 8 different depth for wet weight, dry weight and loss of ignition. Zn, Pb Cd by boiling with HNO3/HCL, 3:1 in one hour and then analysed in an atom absorption spectrophotometer model VARIAN AA-1275. Three double samples were taken inside Farstaviken in a gradient from the wastewater outlet. Four samples were taken in the neighbouring basin to investigate if spreading had occurred out of Farstaviken. One of the cores in each basin was analysed in a "CG Gamma counter" at 15 different levels for Cesium-137. The sediment in the Stockholm archipelago shows a distinct peak at a 4 depth equal to the year 1986 when the Tjernobyl incident occurred. This peak was used to crosscheck the dating of the cores. To compute the dry substance deposition, the density, the dry substance and the thickness of each layer must be known. The density was computed with the following empirical formula (Håkansson, L., Jansson M. 1983): ρ = 260/(100 + 1.6*(W+LOI0)) ρ W LOI0 In which (1) = density (g/cm3) = water content in % = loss of ignition in % of wet substance. The density and the dry substance were interpolated between the known levels and the calculation of yearly dry substance deposition could be done with the following formula: ds-dep = t* ρ * ds * 10 000 (2) ds-dep = dry substance deposition (g/m2/year) t = layer thickness (cm) ds = dry substance (g) In which Corresponding computations were done for the metals and the historical profile of yearly load of Zn, Pb and Cd could be constructed. The accumulation bed in Farstaviken is divided into two deeper areas "Farsta AB" and "Farsta C", figure 2. The deposition in the two sampling points "Farsta A" and "Farsta B", figure 4, were averaged to represent the deposition in area "Farsta AB", figure 2. E 18o23 Farsta C N Farsta B Farsta A N 59o18’,5 Straight Baggen A 1 kilometer FIGURE 4. The soft accumulation areas of Farstaviken and the sampling points "Farsta A", "Farsta B", "Farsta C", "Baggen A". 5 Sampling point "Farsta C" represents the second deep area inside Farstaviken and the sampling point "Baggen A" represents the third deep area, which is situated in Baggensfjärden. To estimate the additional amount of sediment due to factory disposal that has reached the deeper bottoms, all these extra sediments were assumed to have deposited in the first deep area represented by the averaged "Farsta AB" (Zhang., Öberg. 2000). The annual sedimentation in "Farsta C" was assumed to be close to natural background value and could for each year be subtracted from the annual sedimentation in "Farsta AB". To get the total amount of additional settled sediment, this additional annual sedimentation was applied on the accumulation area of "Farsta AB". The same calculation was done for Zn and Pb. In the case of Cd the yearly sedimentation loads show an increased amount of Cd in "Farsta C" during 1980, so the additional annual load of Cd was calculated for both the areas "Farsta AB" and "Farsta C". The subtracted background level used was related to the third deep area "Baggen A" which does not show an increased load of Cd. RESULT Factory Discharge. The production figures of sanitary production was estimated to 100 tons at 1939 and interpolated to 5 000 tons at 1968, which gives a total production of 80 000 tons. This would correspond to a discharge of 8 000 tons, containing 40 tons zinc. The household ceramics production was estimated to 10 tons at year 1836 and 5 000 tons at 1968 (Öberg. 2001), interpolation gives a total production of 100 000 tons. The discharge here would be 10 000 tons with a lead content of 50 tons. Inner Shallow Area. The analysis from the years 1976 (Orrje. 1976), 1984 (VIAK. 1984) and 1999 (Öberg. 2001) are shown in figure 5. mg/kg Zn 4 000 mg/kg 4 000 3 000 3 000 2 000 2 000 1 000 1 000 0 1970 1980 1990 Year 2000 Pb mg/kg 125 Cd 100 75 50 25 0 1970 1980 1990 2000 Year 0 1970 1980 1990 2000 Year FIGURE 5. Concentrations of Zn, Pb and Cd in the inner shallow part of Farstaviken 1976 (6 samples of Pb and 3 samples of Cd), 1984 (6 samples of each) and 1999 (6 samples of each) 6 The concentrations are elevated, for Zn 12 times the background value, for Pb 33 times and for Cd 39 times. The estimated volume of the disposed material is 15 000 m3 (Öberg. 2001 ) and the dry mass 10 000 tons. The additional amount of Zn, Pb and Cd is 20 Zn Pb Cd tons, 9 tons and 360 Year mg/kg mg/kg mg/kg kg respectively. 1999 1 952 861 36 The average 1984 1 850 1 143 54 concentrations of Zn, 1975 2 967 27 Pb and Cd are in the Mean 1 901 1 657 39 same order of magnitude during the Background values 150 50 1,2 25 years that the samples represent. A TABLE 1. Mean concentrations from the decreasing trend can samples in figure 5 and site-specific be seen for Pb. This background concentrations in the inner can indicate that part of Farstaviken (VIAK 1984) washing out of Pb has taken place. The concentration of Zn is about the same in 1999 and in 1984 but Cd shows a different pattern with the highest value at 1984. Deep bottom. The sediment map in figure 4 shows that the total area of sedimentary beds is 0,24 km2 and the area that contain gas in the sediment is 0,13 km2. The area of "Farsta AB" and "Farsta C" were estimated to be 0,12 km2 each. The concentration of metals in the sediment shows the following pattern when plotted against the year of deposition. Concentrations Zn Year Farsta AB Farsta C Baggen A 2000 1990 Concentrations Concentrations Cd Pb Farsta AB Farsta AB Year Year Farsta C Farsta C 2000 2000 Baggen A Baggen A 1990 1990 1980 1980 1980 1970 1970 1970 1960 1960 1960 1950 1950 1950 1940 1940 1940 1930 1930 1930 0 1000 2000 mg/kg 0 1000 2000 mg/kg 0 10 20 30 40 mg/kg FIGURE 6. Concentrations of Zn, Pb and Cd The concentrations of Zn, Pb and Cd show a declining trend away from the factory outlet in recent as well as historical time. Zn shows a peak at the 7 level corresponding to the middle of the 1960’s with max concentrations of 2 000 mg/kg, Pb at the early 1950’s with max concentrations of 2200 mg/kg, Cd at the late 1970’s with max concentrations of 35 mg/kg. The annual sedimentation in the first deep basin of Farstaviken, "Farsta AB", has a peak at a depth corresponding to the early 1960´s with at most 5 kg/m2 after which it declines to about 500 g/m2. In "Farsta C" the yearly sedimentation has declined to 500 g/m2. In Baggen"A", the sedimentation during the last 10 years is 3-5 times higher than in Farstaviken. The additional amount of material that has been deposited in "Farsta AB" compared to "Farsta C" is about 4 000 tons. Year 2000 Year 2000 Dry substance 1990 1990 1980 1980 1970 1970 1960 1960 Farsta AB Farsta C Baggen A 1950 1940 Zn Farsta AB Farsta C Baggen A 1950 1940 1930 1930 0 2 Year 2000 4 2 Year 2000 Pb Farsta AB Farsta C Baggen A 1990 1980 0 6 kg/m 1960 1960 1950 1950 1940 1940 1930 4 6 6 2 g/m Cd Farsta AB Farsta C Baggen A 1980 1970 2 4 1990 1970 0 2 1930 2 g/m 0 20 40 2 mg/m FIGURE 7. Annual deposition of dry substance, Zn, Pb, and Cd in "Farsta AB", "Farsta C" and "Baggen A" Zinc has two peaks in the 1960´s with the maximum peak at 7 g/m2, after 1970 the yearly load of zinc decreases. The additional amount of Zn that has been deposited in "Farsta AB" compared to "Farsta C" is about 10 tons. 8 Lead has its peaks of distribution at a depth corresponding to the early 1960´s. After 1970 the yearly load of lead is decreases. The additional amount of Pb that has been deposited in "Farsta AB" compared to "Farsta C" is about 16 tons. The deposition of cadmium in "Farsta AB" shows two peaks, one during the late 1950’s and one in the early 1970’s with sedimentation loads of 25-35 mg/m2. A smaller peak at 1982 is also visible. "Farsta C has a peak at the beginning of the 1980’s. After 1980 the yearly load of cadmium decreases. The additional amount of Cd that has been deposited in "Farsta AB" and in "Farsta C" compared to "Baggen A" is about 125 kg. TABLE 3. Mass balance for waste material Dry material Zn Pb ton ton ton Disposal from factory 18 000 40 50 Inner shallow area 10 000 20 9 Accumulation area 4 000 10 16 Difference 4 000 10 25 Cd kg 360 125 DISCUSSION The bigger difference for Pb compared to Zn in Table 3 may have an explanation in that the sample cores did not get deep enough to reach background values for Pb, this is indicated in figure 7. Pb is also heavier than Zn and may therefore more remain on the harder bottom between the inner shallow area and the deep accumulation area. As figure 7 shows no vital difference in the yearly load of dry substance in "Farsta AB" and "Farsta C" can be seen after 1975. This lead to the conclusion that no significant amount of sediment has been eroded and transported from the inner shallow area to the inner deep accumulation area after 1975. The estimated amount of sediment in the inner shallow area is then approximately the same in 1975 and in 1999, 10 000 tons. The mean concentration of Pb 1976 and 1999, Table 1, give a difference of 21 tons that may have been resuspended and transported in direction of the deeper accumulation areas. Some explanations for the sedimentation pattern in figure 7 can be that in the production of household ceramics a more refined use of Pb was introduced in the 1950´s because of working health problems. In 1968 Swedish legislation prohibited pollution of natural water systems and the factory built a treatment plant for the wastewater. In 1980 the factory stopped a production line of plastic components, this production used cadmium as UV-stabilisation for the plastic material. The peak of Zn deposition in the 1960´s corresponds well with the increase of production due to the Swedish "million-programme" for construction of houses launched in Sweden. One million apartments were supposed to be built. They all needed a toilet seat. 9 The mass balance of the waste disposal in the basin is uncertain because of a lack of production figures, few bottom samples and material temporarily deposited on hard bottoms and different analysis procedures. It gives however an idea of the order of magnitude and distribution of disposed material including contaminant components, even for a historical discharge. REFERENCES Anonymous. 1998. "Methods of Sedimentologic Investigations in Coast Areas", Uppsala University, Report from PhD student course, Sweden Anonymous. 1998. “Environmental Report of the Gustavsbergs Ceramic Factory", Gustavsbergs Fabriker, report made for the Local Environmental Authority, Värmdö, Sweden Arvidsson, E.S., Aspfors, J., Gullmert, L. 1997. The Ceramic Factory of Gustavsberg, ISBN: 91-971577-3-2. 17-114 Engqvist, A. 1999. Coast and Seas, Swedish Environmental Protection Agency background Report 4910, ISBN: 91-620-4910-0, 10-13 Håkansson, L., Jansson M. 1983. Principels of Lake Sedimentology. Springer-Verlag, Berlin, ISBN: 3-540-12645-7. 316 Lännergren, C., Johansson, P. 1997 Investigations in Stockholm Archipelago 1996. Stockholm Water Company Report. 36, 49-51 Öberg, O. 2001 "Assessment of Sediment Contaminants From Ceramic Production, a Case Study of Farstaviken". Licentiate thesis, Royal Institute of Technology, Stockholm, Sweden. Orrje. 1976. “Investigation of the Inner Part of Farstaviken”. Report made for the Factory of Gustavsberg. VIAK. 1984. “Investigation of the Inner Part of Farstaviken”. Report made for the Swedish National Road Authority. Zhang, Z., Öberg, O. 2000. A Baroclinic Model with Sediment Deposition in a Small Basin in the Stockholm Archipelago. 4th International Conference on Hydro-Science & Engineering , Korea Water Resources Association, Korea 10
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