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Soil Biology & Biochemistry 39 (2007) 13831390 www.elsevier.com/locate/soilbio

Trace and nutrient elements in manure, dung and compost samples in Austria
Manfred Sager
Austrian Agency for Food and Health Safety, Competence Centre for Elements, SpargelfeldstraX e 191, A-1226 Vienna, Austria Available online 26 December 2006

Abstract In Austria, farm animals are estimated to produce about 20 106 ton of excrements annually. In order to predict possible changes of the inorganic compositions of the target soils from various organic fertilizers, mean compositions of excrements, composts and sewage sludges have been compiled on a dry weight basis. Although the high amounts of K and P were benecial, there were some high concentrations of Na in biogas residues and pig manures. Intense additions of Cu, Zn, and Se are reected in high loads in the respective excrements, and these amounts in some instances exceeded the threshold limits for soil contamination. Selenium addition to arable soils can be regarded as benecial, however, as Austria is a low Se area. Composts and sewage sludges were higher in Al and lithophilic trace elements than were the excrements. Factor analysis traced phosphates as the main source of Cd. Cr in processed matrices was signicantly higher, and abrasion from tools should be considered in future investigations. Other unwanted trace elements, like Ni, Pb, As and Hg, were found at a rather low concentration. r 2006 Elsevier Ltd. All rights reserved.
Keywords: Organic fertilizers; Excrements; Composts; Microelements; Animal farming

1. Introduction Austria has currently about 8 106 inhabitants, and 2.75 106 live in rural areas. Some areas house a lot of foreign tourists. In addition, about 2 106 cattle, 3.2 106 pigs and 12 106 chickens are annually produced, as well as lesser amounts of other farm animals. This results in about 20.4 106 ton of excrements annually (Table 1). These might be either deposited as waste, incinerated, used for fertilization, or for biogas production with subsequent use for fertilization. Since the Stone Age, manure and dung have been used to improve soil quality and to recycle phosphorus (P), carbon (C) and nitrogen (N). Animal manure and compost addition increases soil organic matter content, soil aggregate stability, water holding capacity, water inltration and hydraulic conductivity. When a molli-gleyic uvisol of pH 7.6 and 2.07% organic carbon (OC) content was fertilized for six consecutive years either with compost or with
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E-mail address: manfred.sager@ages.at. 0038-0717/$ - see front matter r 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.soilbio.2006.12.015

mineral fertilizers at the same phosphate input amount, no signicant differences in pH, carbonate content, and waterextractable phosphate was observed. Compost treatment, however, increased cation exchange capacity, OC content, and water extractable chloride more than did mineral fertilization (Bartl et al., 2002). Besides maintaining high OC amounts in soils, organic fertilization practice helps the lowering of the eutrophication of surface waters, and saves in the energy for the synthesis of N-compounds needed to stimulate the growth of valuable crops. An effective use of animal waste resources might provide a contribution in reducing net CO2 emissions. Less fossil energy is needed for the industrial production of fertilizers, although some fossil energy is needed for transport and drying (Ceotto, 2005). The main disadvantages are in the entry of toxicants and pathogens to the arable soils. Whereas organic compounds are more or less microbially degradable, metal salts persist and are sparingly transported to deeper layers (Tables 24). Commercial feedstuffs are frequently enriched with essential elements copper (Cu), manganese (Mn), iron (Fe), zinc (Zn), cobalt (Co), molybdenum (Mo) and

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1384 M. Sager / Soil Biology & Biochemistry 39 (2007) 13831390 Table 3 Concentration of zinc in commercial feedstuffs in Austria in the period 20022004; medians of samples taken by the state public authorities
Animal Zn (mg kg1)a Single feeds Supplementary feeds 467 740 405 1787 193 313 341 60 Mineral components 3690 3300 2990 2450 5450 5200 3150 5789 1975 Premixes

Table 1 Estimation of excreta loads annually produced in Austria Animal Production (106 kg y1) 2.05 3.25 Estimated excreta annually produceda 9000 kg per animal (per 500 kg of animal weight) 550 kg per pig and fattening period (3 pigs at 1 place) 1000 kg per 7 sheep (per 500 kg of animal weight) 6 kg per broiler chicken 30 kg annually per place (3 turkeys at 1 place) 103 t y1

Cattle Pigs

18,468 1785
Piglets Pigs Sows Calves Bulls Lactating cows Horses Sheep Poultry Laying hens

153 119

Sheep Chickens Turkeys

a

0.33 12.35 0.55

47 74 5.5

Excreta load values based on wet weight.

92,000 9800

Table 2 Concentration of copper in commercial feedstuffs in Austria in the period 20022004: medians of samples taken by the public control authorities
Animal Cu (mg kg1)a Single feeds Supplementary feeds 535 110 166 87 37 50 38 60 Mineral components 2970 868 759 243 950 950 560 281 13,200 1925 Premixes

a Values estimated as dry weight. The samples have been taken as supplied, but for reasons of stability, the water content of these commercial feedstuffs ranges from about 4% to 8%, with a maximum of 12%.

Table 4 Concentrations of selenium in commercial feedstuffs in Austria in the period 20022004; medians of samples taken by the state public authorities
Animal Se (mg kg1)a Single feeds Supplementary feeds 1.75 1.79 1.44 4.41 0.63 0.68 0.50 2.57 Mineral components 10.5 14.9 11.3 14.3 27.5 27.6 14.7 18.8 11.8 Premixes

Piglets Pigs Sows Calves Bulls Lactating cows Horses Sheep Poultry Laying hens
a

119 37

10.3 18.4

Values estimated as dry weight. The samples have been taken as supplied, but for reasons of stability, the water content of these commercial feedstuffs ranges from about 4% to 8%, with a maximum of 12%.

Piglets Pigs Sows Calves Bulls Lactating cows Horses Sheep Poultry Laying hens

0.38 0.42

563 46.5

selenium (Se) to promote optimum nutrient supply and thus optimum growth rates (Tables 2 and 3). For pigs, the minimum requirement of Cu in the feedstock is in the range 510 mg kg1, but higher amounts stimulate growth. Zinc deciencies may occur in high calcium (Ca) and high phytic acid diets. In intense pig farming, the amount of Cu eliminated through the animal faeces corresponds to 7280% of the amount ingested, and this proportion can be as high as 9296% for Zn (Mantovi et al., 2003). Manures from Germany contained more Cu and Zn than all types of mineral fertilizers. In particular, pig manure contained extraordinary amounts of nickel (Ni). Similarly, in sewage sludges and composts, mean contents of lead (Pb), Cu, chromium (Cr), Ni, and Zn were higher than in mineral fertilizers with respect to nutrient contents. Within the years 19861988, arable soils in Lower Saxony received more inputs of Cu and Zn from various manures, but less inputs of arsenic (As), Cr, and cadmium (Cd) with respect to equivalent mineral fertilization. A tendency towards higher inputs of Pb, Ni, and Se from manures

a Values estimated as dry weight. The samples have been taken as supplied, but for reasons of stability, the water content of these commercial feedstuffs ranges from about 4% to 8%, with a maximum of 12%.

was noticed (Severin et al., 1990). In pig slurry, Pb, Ni, and Cr were below the concentrations encountered in arable soils. In 1998, a change of feeding habits in BadenWu rttemberg led to a mean reduction of 30% for Cu and 20% of Zn in pig slurry, compared to the similar data for 1995 (Siegfried, 1998). In Northern Italy, 1015 years of fertilization with manure from intense pig or cattle farming led to signicant enrichments of Cu and Zn in arable soils. In the Mantova area (Italy), pig slurries can be expected to contain 250800 mg kg1 Cu and 6001000 mg kg1 Zn, and calf slurries to contain 3060 mg kg1 Cu and 6001100 mg kg1 Zn (dry weight). These amounts of Cu and Zn can lead to values of 50220 and 90150 mg kg1, respectively, in arable soils (Mantovi et al., 2003).

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The primary concern associated with land application of sludges centres on the mobility and utilization rates of potassium (K) and P reaching high concentrations. Because the organic phosphates of composts are mineralized during composting, the direct P utilization rates are lower compared with mineral P, and the respective inputs should be considered only in long-term nutrient balances (Pfundtner and Hoesch, 2003). Higher trace metal, sodium (Na) and K amounts from composts do not necessarily lead to higher plant uptake, because plant availability is lower. In particular, Cd transfer to crops has been shown to be signicantly higher from mineral fertilizers than from composts (Bartl et al., 2002). Also, Cu and Zn transfer to edible parts of crops was low from soils contaminated with pig slurries. Cu uptake increased from maize to sugar beet to lucerne, and Zn uptake increased from sugar beet to maize to lucerne (Mantovi et al., 2003). In pig slurry, one-third of the Cu and of Zn contents were found to be bound to macromolecules of 450 kDa. After 3 d of contact with an acid soil, however, the molecular size distribution of Cu-associated moities had changed in favour of lower molecular sizes, and in favour of higher molecular sizes in the cases of the Zn species. Thus, these species were not in equilibrium, but were involved in microbial metabolic processes (Del Castilho et al., 1993). Mobility changes of trace and nutrient elements have been tested via processing of the additives. Upon dilution, the composting of wastewater sludge with about equal amounts of wood chips reduced the extractability of Ni, Pb, and P into 92 mM acetic acid (20:1 ratio), whereas the extractability of Cu and of Mo was increased. Mixing with CaO to pH 12.3, in order to extract ammonium, increased the amounts extractable with acetic acid, except in the case of P. Incineration at 800 1C for at least 4 h increased the mobility of Cu and Mo, but decreased that of Cr, Co, Pb, and Zn (Richards et al., 1997). Austria, a country of rather small structured agricultural units and climatic zones, considers itself to be a rather clean area. Substantial and increasing amounts of crops are obtained from organic farming. A recent compilation of data has been made to document current element concentrations encountered in Austria in various substances utilized for organic fertilization. This provides detailed information to the user and gives background amounts in the cases of samples obtained from more contaminated areas. 2. Materials and methods Within the last few years, in order to match the application rates in the eld with the needs of the plant cover, many manure, dung, and sludge samples from Eastern Austria have been analyzed for their nutrient contents in our laboratory. The digests were obtained after drying and ashing of representative weights sample (about 4 g of dry weight) in

600 ml glass beakers within a mufe furnace for 6 h at 560 1C, and then dissolving the ash in HCl. When Se and sulphur (S) were needed, drying and ashing was carried out in the presence of excess Mg-nitrate. The digests were run for multi-element analysis on the ICP-OES in at least three dilutions (e.g., 1+24, 1+4 and pure) to meet the optimum calibration ranges, and to trace matrix effects. Water contents were determined in aliquots at 110 1C, and all data were nally calculated with respect to concentrations on a dry weight basis. Some data can be compared with a previous study carried out in 19921993, to trace trends which happened within the last 10 y due to changing farming practices, or to changing emissions into the environment. The data from 1992 to 1993 were obtained after a similar sample decomposition procedure, but ame AAS was used. For some other elements, which are easily determined simultaneously using ICP-OES, no previous data are available. Whereas solid dung samples from cattle were used in 19921993, in the present study liquid cattle manure was used, due to obvious changes in farming practices, which may complicate comparisons. 3. Results Respective data from soil inventory and river sediment inventory studies are quoted for comparison in order to interpret the current datasets (Tables 5 and 6) with respect to possible accumulations, both at a global scale and for local arable soils and river sediments. Unfortunately, soil and sediment data cannot be fully compared. The sediments were sieved at 180 mesh ($0.08 mm) and underwent HF digestion (Pirkl and Kralik, 1988), whereas the soils were sieved at o 2 mm, and were digested with aqua regia (Danneberg, 1999) (Tables 5 and 6). 3.1. Main and nutrient elements The mean abundance of K in the Earth crust (which averages down to a depth of 35 km below the continents and to 1013 km below sea level in the large oceans) has been estimated at about 26 g kg1 (Mason and Moore, 1982). Because K is mainly bound to silicates such as muscovite and feldspars, it is sparingly bioavailable. Within this dataset, the highest K concentrations, at 5080 g kg1, were encountered in pig manure and biogas manure. The amounts of K decreased in the order pig manure 4 cattle manure 4 pig dung 4 poultry dung 4 compost. Na from pig manure and biogas residues easily reached more than 20 g kg1, which is an order of magnitude higher than from compost, and may have caused salt stress. Similarly, the Na/K ratio proportion was signicantly higher in pig manure than in cattle manure and compost. In contrast, Ca was lower in the excrements than in compost, and it was highly variable in poultry dung. Poultry feeds may contain much more Ca than for other farm animals to ensure sufcient stability of egg shells.

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1386 M. Sager / Soil Biology & Biochemistry 39 (2007) 13831390 Table 5 Median content of some nutrients and aluminum in organic fertilizers with respect to mean Earth crust concentrationa Element (g kg1) Na K Ca Mg Al Fe P S
a b

Cattle manure 3.59 44.7 20.6 9.3 1.67 1.97 8.4 5.1

Pig manure 2.08 75.5 32.1 14.4 0.70 2.08 28.0 b

Pig dung 2.68 18.6 36.2 11.9 0.76 2.68 29.0 6.0

Poultry dung 2.04 15.0 50.5 6.8 0.45 1.25 19.1 3.5

Biogas manure 16.3 67.1 31.0 7.6 2.2 3.6 13.5 4.6

Compost 0.62 6.2 83.6 15.6 15.1 21.9 5.3

Sewage sludge 2.25 6.8 53.3 17.4 18.9 45.1 10.9 5.5

Mean crust 28.3 25.9 36.3 20.9 81.3 50.0 1.05 0.26

Data expressed as dry weight. Not determined.

Table 6 Median content of some micronutrients and heavy metals in organic fertilizers with respect to mean Earth crust concentrationa Element (mg kg1) Co Cu Mn Mo Se Zn Ba Be Li Sr V As Cd Cr Hg Ni Pb
a b

Cattle manure 2.1 51 180 3.5 0.59 164 46 0.16 3.2 59 2.9 0.33 0.27 6.6 6.3 4.1

Pig manure 4.0 282 358 5.3 3.37 1156 24 0.16 3.5 47 4.2 0.88 0.46 6.9 12.5 1.9

Pig dung 2.3 84 317 2.1 1.35 399 42 0.16 1.4 53 6.0 0.51 0.33 7.8 8.9 2.6

Poultry dung 1.7 66 339 3.3 1.40 314 41 0.17 2.1 60 7.8 0.12 0.43 10.7 8.5 5.4

Biogas manure 2.4 94 289 4.9 0.80 349 35 0.30 7.2 48 5.4 0.56 22.3 14.1 7.7

Compost 7.5 100 447 1.3 b 267 182 1.91 15.9 151 24.7 7.0 0.43 38.3 0.33 25.7 43.4

Sewage sludge 12.8 166 265 1.3 2.08 683 163 2.30 33.3 136 27.7 11.2 0.82 30.6 0.58 25.6 38.3

Mean crust 25 55 950 1.5 0.05 70 425 2.8 20 375 135 1.8 0.2 100 0.08 75 13

Data expressed as dry weight. Not determined.

Mg in pig manure and in pig dung was as high as in compost, whereas Mg was lower in cattle manure, poultry manure, and in biogas manure. Thus, the Ca/Mg ratios were higher in poultry dung and compost than in cattle manure. The quasi total Al (i.e., the Al that is soluble without HF digestion) was signicantly higher in the composts than in the animal products. In other words, whereas Al and Mg in composts were about equal, Al was much less in excreta. The quasi-total Al/Fe ratio varied within the same broad range for all matrices investigated, and contrary to geological samples, did not indicate any special meaning. Sulphur was at about the same concentration for excreta, sludges and composts, and well above mean crust amounts. Mean occurrence of P in the Earth crust is about 1.05 g kg1, which includes mineral phosphates and also metamorphic apatites. P amounts in all excreta were higher, and top concentrations were reached in pig dung and pig manure, although still less than present in most mineral NPK fertilizers. The K/P ratio was highest in cattle

manure, and lowest in pig and poultry dung. The excreta of herbivore cattle signicantly differed from the plantderived composts in K/P and Ca/Mg ratios. 3.2. Essential trace elements In stream sediments, Zn is a good indicator of anthropogenic inputs. Likewise, all excreta investigated, and sludges and composts were above the mean crust amounts of 70 mg kg1 for soils. Arable soils of Austria have mean values between 56 and 89 mg kg1. For Zn, 300 mg kg1 is considered to be the soil contamination threshold. Sewage sludges may contain some Zn from the abrasion of Zn-plated metals and roofs, but the Zn contents found in pig excreta and poultry manure were even higher. Whereas the mean concentration in sediments of moderately polluted rivers in the lowlands around Vienna was within 100200 mg kg1 (Pirkl and Kralik, 1988), the mean in this work for pig manure was almost 1200 mg kg1, and that falls within the category of

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hazardous waste. Metal enrichments in the target soil should thus be taken into consideration. For Cu, the mean abundance in the entire Earth crust has been estimated at 55 mg kg1, and the threshold limit for contamination in soils is 100 mg kg1. In Austria, a lot of uncontaminated river sediments are around the mean crust concentration, but due to contaminations, up to 332 mg kg1 were found in the local rivers Triesting and Piesting (Pirkl and Kralik, 1988). Median Cu in Austrian arable soils was around 20 mg kg1 (Danneberg, 1999). Whereas cattle excreta were at mean crust concentrations, composts were slightly higher, and sewage sludges were signicantly higher. Cu was found to be extremely enriched in pig and poultry manure, and even more so than in sewage sludges, and concentrations varied within a broad range. This may be the result of feeding farm animals with the essential element Cu at the upper tolerance limit (Table 2). For all kinds of farm animals, manure samples were higher than for the corresponding dung samples. For a long time Mo has been accumulating in biota and coals. It was found mainly at above mean crust concentrations of 1.5 mg kg1, except in the cases of composts, which were within the range commonly found in green plants. In Austrian soils, medians of Mo concentrations ranged between 0.2 and 0.7 mg kg1. As some crops may have requirements for Mo, addition of Mo to the soil seems benecial. The contamination limit of 5 mg kg1 is hardly reached, however. Mean Se in Austrian soils was determined to be 0.23 mg kg1, which is quite low with respect to the needs for animal and human nutrition. All types of excreta and sewage sludges were above this concentration. As was found for Cu, Zn and P, Se concentrations were highest in pig manure, at a median of 3.4 mg kg1. No data were available for the compost samples (Table 7). For the essential trace elements, it may be worthwhile to consider also the elemental ratios Cu/Se, Mn/Se, and Zn/ Se, because these pairs might act as antagonists in cell metabolism. The Cu/Se ratios between different organic waste types were largely overlapping. These, due to low Se, were highest in biogas residues, whereas due to high Se, they were lowest in sewage sludges. Zn/Se elemental ratios were widely overlapping and within the range encountered

in soils. The S/Se ratios were signicantly lower in excreta than in cereals, mainly because of low Se concentrations in the cereals. Among the excreta, S/Se was higher in biogas residues than in pig and poultry manures, possibly because of gaseous losses of Se. Unfortunately, no Se data were available in the cases of compost samples, and there were no data for S for the manure and dung samples. Due to low Mn contents in animal tissues, the mean abundance in the Earth crust of 950 mg kg1 was not reached in manures and dung samples, and barely in composts. It varied widely in sewage sludges. Cattle manure was lowest. In case high Mn is needed, Mn concentrations in composts will be increased from additions of tree barks.

3.3. Elements of low biological signicance Elements of low or even non-existent fertilizer requirements are met by organic fertilizers far below their abundance in the roughly 35 km deep continental global shell, such as Al, Ba, Be, lithium (Li), Sr, and vanadium (V). Composts and sewage sludges contained more Sr and Ba than excreta. Correlations with Ca, which would be geochemically feasible, were not found. For Li, the mean crust abundance is 20 mg kg1, but major parts are bound to silicates and are thus not soluble without HF digestion. As in many feedstuffs and tissues, Li was minor, 5 mg kg1, in the excreta, and was thus very low. It may be higher in biogas residues, and reach around 20 mg kg1 in composts, which resembles the amounts met in limestones and sandstones. Whereas Be in composts was approximately close to the mean Earth crust amount, it was very low and rather constant in all types of excreta. Most excreta had of the order of 10 mg kg1 of V, and that value was very low compared with the mean crust abundance of 135 mg of V kg1. V was not investigated in the soil inventory, but in river sediments it varied between 5 and 142 mg kg1. Although V in most green plants is in the range of 0.10.2 mg kg1, the amounts in composts and sewage sludges were signicantly higher than in the excreta, at about 30 mg kg1. Appreciable amounts, however, might

Table 7 Some nutrients and ratios among elements found in organic fertilizersa Element Cu (mg kg1) Mn (mg kg1) Se (mg kg1) Zn (mg kg1) Cu/Se ratio Mn/Se ratio Zn/Se ratio
a b

Cattle manure 51 (8117)b 180 (40312) 0.59 (0.120.84) 164 (49405) 92 (61189) 397 (671245) 470 (82780)

Poultry dung 66 (28182) 339 (91807) 1.40 (0.543.19) 314 (92739) 75 (21175) 482 (2871538) 226 (163693)

Pig dung 108 (23211) 307 (74481) 1.35 (1.081.42) 710 (481439) 79 (44140) 297 (244310) 448 (2791015)

Biogas residue 94 (1360) 289 (41530) 0.80 (1.153.36) 349 (141715) 132 (54336) 307 (872895) 537 (2811154)

Sewage sludge 166 (10612) 265 (211941) 2.08 (0.2713.1) 683 (451575) 58 (4482) 131 (15485) 320 (302891)

Pig manure 282 (27642) 358 (93907) 3.37 (2.013.57) 1156 (2141693) 76 (15441) 137 (28554) 325 (641751)

Data expressed as dry weight. Values in parentheses refer to minimum and maximum values found, respectively.

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not dissolve in the HCl extracts of the ashes, compared to incomplete recovery from aqua regia digests. 3.4. Unwanted trace elements Cadmium has been a favourite indicator element for anthropogenic pollution sources, and thus it is very often investigated. Although the geochemical Cd/Zn ratio is within the range of 1:3001:1000, the main Cd sources in agriculture are not Zn salts but certain phosphate ore deposits, because Cd can substitute for Ca in the apatite lattice. Whereas the median Cd concentrations found in Austrian soils are at the same concentration as the mean of the outer shell of the planet Earth itself of 0.2 mg kg1, many organic fertilizer samples are higher, but still below 1 mg kg1, which is regarded as the threshold of contamination. Local river sediments also contained 0.20.9 mg kg1. Like Cd, Pb has been indicative of anthropogenic inputs since prehistoric times. Medians of Pb in arable Austrian soils ranged between 6 and 33 mg kg1, but 12466 mg kg1 were found in local river sediments. Excreta were far below the mean Earth crust concentrations of 18 mg kg1. Biogas residues contained around 8 mg kg1, which is the range for limestone. Composts and sewage sludges were above mean crust amounts. Higher Pb concentrations in composts may result from atmospheric precipitation on plant leaves. Arable soils usually get a much higher Pb load from atmospheric precipitation than from fertilizers (Sager, 1997; Sager and Scholger, 2002). The Pb/Cd ratio in composts was within the range expected from the respective mean abundances, whereas due to high Cd and low Pb, the ratio was low in the excreta. This ratio was intermediate in sewage sludges. All Pb/Cd ratios were similar to the Fe/Mn ratios; that may have been fortuitous, and no reason can be given for it at this time. Local river sediments contained 16286 mg kg1 total Cr. For soils and sediments, only 30% of the Cr is soluble in aqua regia. This discrepancy is much lower for composts and sludges, which do not contain chromites, garnets and other Cr-bearing minerals. Cr in excreta was about 10 mg kg1 and thus rather low; among the excreta, it was highest in poultry dung. Abrasion from chromiumcontaining cages might be a possible source, but that should be considered in further studies. Chromium varied widely in biogas residues, possibly due to abrasions from mixing tools. Composts and sewage sludges contain more

Cr than manure and dung samples, but still less than the mean Earth crust level. Thresholds set for Ni in agriculture have been close to the mean Earth crust abundance of 75 mg kg1, and that concentration was not reached in any of the applications. Medians in arable soils were within 829 mg kg1, but contaminated river sediments contained up to 163 mg kg1. Whereas Ni in green plants is usually in the range of 12 mg kg1, it was at about 26 mg kg1 in the composts, and that is within the same range as in sewage sludges. Among the excreta, Ni was higher in pig manure and biogas residues, but still lower than in the sewage sludges and composts. Signicant amounts of V, as well as Cr and Ni, may also be derived from the abrasion of tools used in the production of composts or biogas. Mercury (Hg) was determined only in compost and sewage sludge samples, and it appeared to be contained only at a moderate amount. 3.5. Statistical evaluations For statistical evaluations, the datasets were grouped in poultry + pig dung samples, cattle + pig manure samples, residues from biogas production, and composts. The correlation patterns seem quite different. In the excreta, nutrient trace elements tend towards higher, whereas lithogenic elements tend towards lower numbers of signicant correlations; this was not the case for composts. In poultry + pig dung samples, many binary correlations were found for Se, Ni, and Fe (12, 11, and 10 correlations from a total of 23 possible ones). This comprises some siderophilic and lithophilic elements. Just one signicant binary correlation was found for Cd, K, Mg, Mn and Na, which would thus seem to enter the dung accidentally. With respect to correlations in cattle + pig manure samples, Cu(11), Ca(10) and Zn(9) were linked most. No signicant binary correlations were found for Al, Cr, Li, Pb, and Sr in the manures. The residues from biogas production are mainly of cattle or pig origin. Biogas production should not change most elemental proportions, as most of the inorganic matrix is not volatile during methane production. Within the given dataset, the maximum number of signicant binary correlations were obtained for Ni, V, and Se (11 out of 23 possibles). None, or just one correlation emerged for Al, Ba, Fe, Mg, Mn, Na, and Pb.

Table 8 Factor weights 40.7 obtained from factor analysis, after rotation Organic fertilizers Poultry + pig dung Cattle + pig manure Biogas residues Composts
a

Factor 1 PbSeBaFeNi MnMoCaCoZnCu SeCoMoZnCuNiPVCdS PZnAlCuMoFeCdCa

Factor 2 AlCoBeLi CdPV LiCr MgNiCrV

Factor 3 MnPCd NaAsSe FeBe PbBaLi

Factor 4 SrAsMg CrLi BaAl NaMnK

Factor 5 CrMn Sr Mn

Factor 6 a Pb MgPb

No value.

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In order to recognize common components and possible differences, the four groups of data were separately submitted to factor analysis. After rotation, almost all elements had at least one factor weight in one component larger than 0.6; only in the case of the biogas residues, Ca, K and Na were not distinctly assigned. This may reect their heterogenous origins (Table 8). In all cases, Cd and P were found together, indicating that Cd enters the food chain via the phosphates. The essential trace elements CuCoMoZn also appeared together, except for the poultry + pig dung. In the latter case, some occasional inputs of misplaced soil might have nullied this connection. Lithophilic combinations, like FeNi, AlBeLi, SrMg, CrMn in poultry and pig dung support this hypothesis. NickelCrV might have a common source in the composts, i.e., the abrasion of tools. In contrast to the composts, NaK were not together in the animal waste samples. Unwanted contaminants Pb and As, and also Mn, were found in different factors in the subsets, which indicates that they were randomly distributed. 3.6. Long term trends Whereas outputs from cattle remained at the about the same amounts, a slight trend towards higher concentrations was observed in pig and poultry dungs. When the data sets get assorted for elements, Cd decreased, but some yers may still occur. Lead, Cr and Ni remained at about a constant level. Copper and Zn showed a tendency to increase (Tables 9 and 10).

Table 10 Comparison of current data of copper, nickel, lead, and zinc vs. values found in 1992/1993a Organic fertilizer Cu (mg kg ) Poultry dung Pig dung Cattle dung vs. manurec Ni (mg kg1) Poultry dung Pig dung Cattle dung vs. manure Pb (mg kg1) Poultry dung Pig dung Cattle dung vs. manure Zn (mg kg1) Poultry dung Pig dung Cattle dung vs. manure
a b 1

1992/1993 41 (2369)b 75 (14177) 34 (13100) 5.2 (3.87.1) 4.5 (1.17.5) 5.7 (2.015.6) 5.0 (1.07.5) 3.0 (0.46.2) 3.2 (0.68.1) 280 (176400) 290 (112944) 148 (41235)

20032005

66 (38182) 62 (23211) 51 (8117) 8.5 (3.419.2) 8.9 (6.210.3) 6.3 (3.98.6) 5.4 (0.219.3) 5.0 (1.911.9) 4.1 (0.46.0) 314 (92739) 399 (481439) 164 (97405)

Data expressed as dry weight. Values in parentheses refer to minimum and maximum values found, respectively. c Explanation of the term cattle dung vs. manure; no cattle dung was available from 2003 to 2005, thus cattle dung from 1992 to 1993 had to be compared with cattle manure from 2003 to 2005.

4. Discussion In organic farming practices, it is necessary to supply the plant needs for the maintenance of steady growth by the addition of composted plant residues. In Austria, domestic animals are considered to produce more than 20 t of excreta annually, and it is worthwhile to consider possible accumulations of unwanted elements in the treated arable soils, and in the crops produced on them. In regions without animal production, a lot of compost of presumably plant origin can be generated. Thus a compilation of the respective data should serve as a fundamental tool of risk assessment. Excreta are expected to introduce more Na, K, and P, but less Ca and Al to the soil than composts. They are still lower in P and in K than most mineral fertilizers, although signicantly lower than most composts. P deciencies are at best overcome with pig and poultry dung, whereas cattle manure yields the highest input of K with respect to other main elements. To satisfy plant needs for high Mg, compost would seem preferable, as pig manure and dung also introduce a lot of Na to the soil. There was no difference between any type of organic fertilizer within this range of materials with regard to requirements to meet high S needs. 5. Conclusions As well as the known contamination sources such as mining, industry, and trafc, high additions of essential elements to the commercial feeds used in modern animal

Table 9 Comparison of current data of cadmium, cobalt, and chromium compared with values found in 1992/1993a Organic fertilizer Cd (mg kg ) Cattle manure Pig manure Poultry dung Pig dung Cattle dung vs. manurec Co (mg kg1) Poultry dung Pig dung Cattle dung vs. manure Cr (mg kg1) Poultry dung Pig dung Cattle dung vs. manure
a b 1

1992/1993 (0.102.95)b (0.222.08) (0.080.82) (0.040.67) (0.080.55)

20032005

0.48 0.86 0.26 0.17 0.21

0.27 0.46 0.43 0.33 0.27

(0.180.44) (0.020.64) (0.190.93) (o 0.020.38) (0.180.44)

2.10 (1.233.89) 1.2 (0.61.6) 2.4 (1.13.4) 4.6 (2.96.0) 6.7 (1.616.1) 8.7 (2.839.5)

1.71 (1.003.43) 2.27 (1.753.07) 2.1 (0.76.5) 10.7 (1.623.1) 7.8 (4.913.2) 6.6 (2.5 7.4)

Data expressed as dry weight. Values in parentheses refer to minimum and maximum values found, respectively. c Explanation of the term cattle dung vs. manure; no cattle dung was available from 2003 to 2005, thus cattle dung from 1992 to 1993 had to be compared with cattle manure from 2003 to 2005.

ARTICLE IN PRESS
1390 M. Sager / Soil Biology & Biochemistry 39 (2007) 13831390

production processes may also pose threats of metal accumulations in organically fertilized soils. Thus, in general, the amounts of Cu, Zn, Mo and Se in all types of excreta were generally above the means of occurrence in the Earth crust of about 35 km thickness below the continents. Some inputs of Se will be benecial for low Se areas, like Europe. Residues from biogas production are rather new for Austrian users. These residues also contained amounts of Cu, Mo, Zn, and Se above the general soil concentrations. Among the unwanted trace elements, Cd and Hg have been found to be enriched with respect to their mean abundance in the entire Earth crust, but at tolerable ambient amounts. For purposes of control, it might be more reasonable to look for Cu and Zn, as well as for Cr from abrasions of tools, and for high Na in certain manures, than for the classical elements Cd, Pb, and Hg, which seem to be under good control. Although controls of metal contents have been in place for many years, and the main industrial emission sources are kept under control in Austria, the occurrence of some heavily contaminated samples (termed as yers) justify a steady and continuous level of monitoring. Whereas the trends of general metal contaminations went down within the last decade, surprisingly, upward trends were noted for some metal amounts in manure and dung samples.

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Acknowledgments We acknowledge and greatly appreciate the help of Ing. Jozo Orec for preparing most of the digests, Mrs. Gabriele Furian for help in the operation of the ICP-OES, DI Erwin Pfundtner for collecting many of the manure and dung samples and DI Gerhard Burdicek for collecting the compost samples.