Disposal of Domestic Sludge and Sludge Ashes on Volcanic Soils Mauricio Escudeya*, Andrew C. Changb, Juan E. Förstera, Juan P. Becerraa, Magdalena Quinterosa, Justo Torresa and Gerardo Galindoa a Facultad de Química y Biología, Universidad de Santiago de Chile Av. B. O’Higgins 3363, Santiago, Chile. E-mail: mescudey@lauca.usach.cl 2 Department of Environmental Sciences, University of California, Riverside CA E-mail:acchang@ucr.edu Abstract Column leaching experiments were conducted to test the ability of volcanic soils in Chile in retaining the mineral constituents and metals in sewage sludge and sludge ash that were incorporate into the soils. Relatively small amounts of the mineral constituents such as Na, Ca, Zn, phosphorus and sulfate in the sludge and sludge ash were readily soluble. When they were incorporated in to the surface layer of the soils and leaching with 12 pore volumes of water over a 3 month period of time, significantly small amounts of the readily soluble constituents were recovered in the drainage water. The volcanic soils were capable of retaining the mineral constituents, phosphorus, and metals in applied sewage sludge and sludge ash and gradually release them as nutrients for plant growth. Keywords: Sewage sludge, sludge ashes, column studies, volcanic soils. 1. Introduction Sewage sludge is the inevitable end product of municipal wastewater treatment processes worldwide. As the wastewater is being purified, the impurities removed from the water stream are being concentrated. The sludge stream thus contains many chemical and microbiological constituents usually in concentrated forms that may become potential sources of pollutants when the material is released. No matter how many treatment steps it undergoes, at the end, the sludge and/or its derivatives require the ultimate disposal. For disposal, the sewage sludge may be land applied, land filled, incinerated, or ocean dumped. There is not an entirely satisfactory solution and all of the currently employed disposal options have serious draw backs. Land application however is by far the most commonly used method around the world. Approximately six million dry tons of sewage sludge is produced annually in the United States. (Bastian, 1997). Recent report showed that the annual production of sewage sludge in member countries of the European Union may reach as much as 8 x 10 6 tons (Bonnin, et al., 2001). Significant amounts of sewage sludge produced in the United States and the western European nations have been applied on land. Dependent on the regions, 24 to 89% of the sludge produced in the U.S. has been applied on land (Bastian, 1997). Bonnin (2001) reported that 65% of the sewage sludge in France was land applied. The situations in other parts of the world are expected to be similar. As the residue of municipal wastewater treatment, sewage sludge represents the aggregation of organic matter, pathogens, trace elements, toxic organic chemicals, essential plant nutrients, and dissolved minerals originally dispersed in the wastewater and are captured and transformed by the wastewater treatment processes. Properly managed, the potential pollutants are assimilated via the biochemical cycling processes of the receiving soils in the land application. The practice provides soils with organic materials and offers the possibility of recycling plant nutrients, which in turn, improve the fertility (Walter and Cuevas, 1999) and physico-chemical properties of agricultural soils (Illera et al., 2000). If not appropriately controlled, the potential pollutants released through the land application may degrade the quality of downstream water bodies, be transferred through the food chain to harm the consumers of harvests, and drastically alter the physical and chemical properties of the receiving soils. It is imperative that mass input provides adequate amounts of substances that are useful to plant development and the pollutant inputs are controlled to avert detrimental public health and environmental effects. Major countries such as the U.S., the European Union (http://europe.eu.int/comm/environment/sludge), and China (Qiao et al., 2000) had enacted regulations or issued guidelines that limited the disposal options for a variety of reasons. Before the treatment works are gradually being brought online in recent years, the collected wastewater in Chile was directly discharged and sewage sludge did not exist. With the commencement of wastewater treatment, sewage sludge and ashes of the incinerated sewage sludge are accumulating in the metropolitan areas awaiting final disposals. As the treatment works handles mainly the domestic sewage, the levels of toxic pollutants were negligible. Land application is the primary option under consideration. The agricultural soils in Central Chile where most of the country’s population centers are situated are derived from parent material of volcanic origin. The predominant minerals of these soils are allophone and ferrihydrite in the Andisols and kaolinite, hollysite and amours iron oxides in Ultisols. These soils were rich in iron oxides and organic matter contents and possessed pH-dependent variable surface charge. However, the soils have poor fertility. At the indigenous acidic pH range of 4.5 to 5.5, the soil has low capacity for exchangeable cations. Phosphorus is strongly fixed by the primary minerals thus is not readily available for plant absorption in these soils. To be productive, they require frequent adjustments of soil pH, replenishments of exchangeable Ca2+ and Mg2+ ions, and heavy phosphate applications. Municipal sewage sludge and ashes of the incinerated sewage sludge appear to possess the essential plant nutrients and dissolved minerals and the buffering capacity (Eriksson, 1998; Zhang et al., 2002ab; Pasquini and Alexander, 2004). When land applied, they may replenish the depleting nutrient reservoirs in these soils under cultivations. If the added constituents are retained in the soils and absorbed by plants, the risk of contaminating the downstream water bodies may be minimized. In this study, the capacity of volcanic soils to retain chemical constituents in the land applied sewage and sewage sludge ash was investigated. Methods and Procedures Soils The surface 0 to 25 cm depth layers of 5 volcanic soils located in the agricultural regions of the Southern Central Chile were collected. Namely, they were Collipulli, Diguillin, Nueva Braunau, Metrenco, and Ralún reflecting the localities from where soils were extracted. The samples were obtained from well drained and regularly cultivated fields. By soil classification, Collipulli and Metrenco are Ultisols and Ralún, Diguillin, and Nueva Braunau are Andosols. General information on the climate and geography of the soils may be found in Escudey et al. (2001). Soil samples were screened in the field to pass a screen with 2 mm openings and stored at the field moisture content in a 4oC cold room until used. Experiments Soils were air dried and packed into columns to the depth of 25 cm according to their respective field bulk densities. Dependent on the treatment, thirty grams of air dried sewage sludge or the ashes equivalent of 30 grams of air dried sewage sludge were incorporated into the surface 5 cm of the packed columns. The experimental controls received neither the sludge nor the ash treatment. Following the treatments, the columns were irrigated weekly with one pore volume of distilled water and gravity drained, for a period of 12 weeks. In addition, 30 grams of sludge and the ash equivalent of 30 grams of sludge were leached in the same manner. The drainages from each weekly leaching cycle were accumulated for analyses of pH, electrical conductivity, SO42- and PO43-. At the end of the leaching experiment, each soil column was cut open lengthwise and the profile was sectioned into five equal length segments for analyses of the soils’ pH, electrical conductivity, and organic carbon, exchangeable cations, and phosphorus contents. Chemical Determinations The bulk density, exchangeable cations, and organic carbon content of the soils were determined by methods outlined in the Methods of Soil Analysis. Part 3 (American Society of Agronomy, Madison, WI). Briefly, the bulk density was determined by the average air dried weight of soils in undisturbed soil cores of the 0 to 25 cm soil profile in 5 cm (dia meter) x 5 cm (height) brass rings; the exchangeable cations were determined as the concentrations of Na, K, Mg, and Ca in ammonium acetate extracts; and organic carbon was determined by measuring the chromic acid oxidized fractions of soils. The pH and electrical conductivity of soils was measured in soil suspensions with soil to water ratio of 1: 2.5 w/v. The total elemental contents of Na, K, Mg, Ca, Zn, Cu, Fe, Al, P and S were determined digesting the soils with a concentrated HNO 3 -HCl-HF mixture in a microwave and measuring the concentrations by ICP-OES spectroscopy. Comparable components of the sewage sludge and sludge ash were determined in the same manner. The SO42- and PO43concentrations in the drainage water were measured by ion chromatography. Results and Discussions Soils, Sludge, and Sludge Ash Prior to the sludge and ash treatments, the soils were acidic with pH varying from 4.5 to 5.9 and low in exchangeable bases contents varying from 1.5 to 10.4 cmol kg-1 (Table 1). In contrast, the sewage sludge and sludge ash had pH of 7.7 and 7.4, respectively that were 2 to 3 orders magnitude higher in alkalinity than those of the soils. The exchangeable base content of the sewage sludge was 34.5 cmol kg-1, 3.5 to 10 times those of the soils. The Na, K, Mg and Ca in the sludge ash were soluble but not necessary in the exchangeable forms. Judging by their electrical conductivities, the soluble mineral contents of ash were orders of magnitude larger than the soils. The total elemental contents of the Ca, Mg, K, and Na in soils follow the same trends as those in the exchangeable forms and the concentrations are in the same order of magnitude. Table 1. Properties of Soils, Sewage Sludge and Sludge Ash Soil Collipulli Metrenco Ralún Diguillin N. Braunau Sludge Sludge Ash pH 5.4 5.5 4.5 5.9 5.5 7.7 7.4 Bulk Density (g cm-3) Organic Carbon (%) Electrical Conductivity (S m-1) Exchangeable Bases (cmol kg-1) Na K Mg Ca 1.36 1.33 0.90 1.12 0.82 0.46 - 2.3 1.8 5.0 5.0 11.4 17.8 <0.1 81 29 436 94 20 8520 3890 0.1 0.2 0.1 0.2 0.1 2.7 - 0.2 0.3 0.1 0.7 0.1 1.6 - 1.8 1.5 0.4 1.1 0.2 7.6 - 5.9 4.0 2.5 8.4 1.1 22.6 - Releases from Sludge and Sludge Ash When the sludge and sludge ash were leached, the soluble Na and SO42- were released quickly (Figure 1). Judging from the shapes of the break through curves (Figure 1), the soluble sodium and sulfate in sewage sludge were depleted with one pore volume of water used to leach the soils. On the other hand, the soluble sodium and sulfate in sewage sludge ash gradually release with 5 to 8 pore volumes of water. The quantities of Na and SO 42- released from the sludge and sludge ash however were comparable, amounted to 19 vs. 16 mg for Na and 342 vs. 319 mg for SO42- (119 vs. 106 mg as S), respectively. The releases were considerably less than the total amounts in the respective material. The phosphorus in sludge and sludge ash released slowly and released at constant rates over time (Figure 2). At the end of 12 leaching cycles, 24 and 7 mg of phosphate were 14 Sodium Release Na in Leachate (mg/L) 12 Sew age Sludge 10 Sew age Sludge Ash 8 6 4 2 0 0 2 4 6 8 10 12 Cumulative Leachate Volume (L) 350 Slufate in Leachate (mg/L) Sulfate Release 300 Sew age Sludge 250 Sew age Sludge Ash 200 150 100 50 0 0 2 4 6 8 Cumulative Leachate Volume (L) 10 12 Figure 1. Releases of Sodium and Calcium from Sewage Sludge and Sludge Ash recovered from the drainages, respectively in contrast to the total amounts of 109 and 121 mg, respectively. The patterns of zinc releases for the sludge and sludge ash were similar (Figure 3). However, the amounts released by the sludge, 0.82 mg, were considerably higher than that of the sludge ash, 0.02 mg. Nevertheless, they were far below the total amounts of 9.6 and 9.8 mg in the sludge and sludge ash, respectively. 30 P Release Cumulative P Leached (mg) 25 Sew age Sludge 20 y = 2.098x Sew age Sludge Ash 2 R = 0.99 15 10 5 y = 0.587x 2 R = 0.91 0 0 2 4 6 8 10 12 Cumulative Leachate Volume (L) Figure 2. Phosphorus Release of Sewage Sludge and Sludge Ash 0.35 Zinc Release Zn in Leachate (mg/L) 0.30 Sew age Sludge Sew age Sludge Ash 0.25 0.20 0.15 0.10 0.05 0.00 0 2 4 6 8 Cumulative Leachate Volume (L) 10 12 l Figure 3. Zinc Release from Sewage Sludge and Sludge Ash In all, only small amounts of the Na, SO42-, P, and Zn were released when the sludge and sludge ash were subject to intense leaching for 12 weeks. Soil Attenuation Even without the applications of sludge or sludge ash, significant amounts of cations and anions such as Ca2+ such as SO42- maybe leached from the soils (Figure 4) and the amounts collected in the drainage water were dependent on conditions of soils. Sludge and sludge ash amendments consistently enhanced the leaching of minerals. However, the incremental increases were significantly smaller than the total amounts added through the addition of sludge and sludge ash. Judging from the break through curves, the releases were spread out over 3 to 4 pore volumes of drainage water. Soil incorporation further reduced the mobility of the chemical constituents in the sludge and sludge ash (Figure 5). For phosphorus and zinc, the amounts found in the drainage water (Figure 5) were 2 to 3 orders of magnitude lower 30 Calcium Leached Calcium (meq/column) 25 Control Sludge-treated Ash-treated 20 15 10 5 0 Collipullli Metrenco Diguillin N. Braunau Ralún N. Braunau Ralún 50 Sulfate Leached 45 Control 40 Sludge-treated Sulfate (meq/column) Ash-treated 35 30 25 20 15 10 5 0 Collipullli Metrenco Diguillin Figure 4. Calcium and Sulfate Leached from Sewage Sludge and Sludge Ash Treated Soils that the amounts present in the added sludge and sludge ash. As a result, nutrients such as the available phosphorus significantly increased with the application of sewage sludge and sludge ash for both the Ultisol and Andisol (Figure 6). 7 Zn Leached 6 Control Zn ( eq/column)) Sludge-treated 5 Ash-treated 4 3 2 1 0 Collipullli Metrenco Diguillin N. Braunau Ralún 1.4 P Leached Control 1.2 Sludge-treated Ash-treated P (eq/column) 1 0.8 0.6 0.4 0.2 0 Collipullli Metrenco Diguillin N. Braunau Ralún Figure 5. Zn and Phosphate Leached from Sewage Sludge and Sludge Ash Treated Soils Conclusions Results of column leaching experiments showed that volcanic soils in Chile were capable of retaining the inorganic mineral constituents, phosphorus, and zinc in sewage sludge and sludge ash when land applied. These constituents are representatives of inorganic minerals, nutrients, and metals that often associated with the municipal sewage sludge. In this regard, the volcanic soils will attenuate the sewage sludge borne pollutants and provide soils with nutrients that may be slowly released for crop production. 60 Diguillin Available P (mg/kg) 50 Control Sludge-treated 40 Sludge ash-treated 30 20 10 0 0 - 5 cm 5 - 10 cm 10 - 15 cm 15 - 20 cm 20 - 25 cm Soil Depth 70 Metrenco Available P (mg/kg) 60 Control 50 Sludge-treated Sludge ash-treated 40 30 20 10 0 0 - 5 cm 5 - 10 cm 10 - 15 cm 15 - 20 cm 20 - 25 cm Soil Depth Figure 6. 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