| Literature DB >> 27687184 |
Abstract
The paper deals with effects of liming and different doses of municipal sewage sludge (5, 10, and 15 % of soil mass) on copper speciation in soil. In all samples, pH was determined together with total copper concentration, which was measured with the ICP-AES method. Concentration of copper chemical fractions was determined using the seven-step procedure of Zeien and Brümmer. In the soil treated with the highest dose of sludge (15 %), there was, compared to the control, a twofold increase in the concentration of copper and a threefold increase in the concentration of nitrogen. Copper speciation analysis showed that in the municipal sewage sludge the easily soluble and exchangeable fractions (F1 and F2) constituted only a small share of copper with the highest amount of this metal in the organic (F4) and residual (F7) fractions. In the soil, at the beginning of the experiment, the highest share was in the organic fraction (F4), the residual fraction (F7) but also in the fraction where copper is bound to amorphous iron oxides (F5). After 420 days, at the end of the experiment, the highest amount of copper was mainly in the organic fraction (F4) and in the fraction with amorphous iron oxides (F5). Due to mineralization of organic matter in the sewage sludge, copper was released into the soil with the share of the residual fraction (F7) decreasing. In this fraction, there was much more copper in limed soil than in non-limed soil.Entities:
Keywords: Copper mobility; Liming; Sewage sludge; Soil; Zeien and Brümmer method
Mesh:
Substances:
Year: 2016 PMID: 27687184 PMCID: PMC5042973 DOI: 10.1007/s10661-016-5609-4
Source DB: PubMed Journal: Environ Monit Assess ISSN: 0167-6369 Impact factor: 2.513
Concentration of chemical elements and pH of the sludge
| DM % | pH | Corg g kg−1 | C:N | N | P | K | Ca | Mg | S | Na |
| g kg−1 dm | ||||||||||
| 25.0 | 6.8 | 345 | 8.6:1 | 40.00 | 21.23 | 2.78 | 38.56 | 8.41 | 5.23 | 0.854 |
| Fe | Mn | B | Mo | Co | Pb | Cd | Cr | Cu | Zn | Ni |
| mg kg−1 dm | ||||||||||
| 7984 | 521 | 8.96 | 4.21 | 3.80 | 50.23 | 0.174 | 19.85 | 85.01 | 1120 | 50.14 |
Sequential extraction of heavy metals with the Zeien and Brümmer method
| Fraction | Name | Extraction reagent | Extraction time | pH |
|---|---|---|---|---|
| F1 | easily soluble | 1 mol NH4NO3 dm−3 | 24 h | natural |
| F2 | exchangeable | 1 mol CH3COONH4 dm−3 | 24 h | 6.0 |
| F3 | bound to MnOx | 1 mol NH2OH HCl dm−3 + 1 mol CH3COONH4 dm−3 | 0.5 h | 6.0 |
| F4 | Forg bound to organic matter | 0.025 mol C10H22N4O8. dm−3 | 1.5 h | 4.6 |
| F5 | bound to amorphous FeOx | 0.2 mol (NH4)2C2O4 dm−3 + 0.2 mol H2C2O4 dm−3 | 4 h | 3.25 |
| F6 | bound to crystalline FeOx | 0.2 mol (NH4)2C2O4 dm−3 + 0.2 mol H2C2O4 dm−3 + 0.1 mol C6H8O6 dm−3 | 0.5 h | 3.25 |
| F7 | Fresid residual | Calculated as the difference between the total content of a particular heavy metal and the sum of the above determined fractions | – | – |
Soil proportion/solution 1 g:10 cm3
Total concentration of nitrogen (mg kg−1) in soil in the incubation experiment
| Days | 0 | 5 % | 10 % | 15 % | Mean | 0 | 5 % | 10 % | 15 % | Mean |
|---|---|---|---|---|---|---|---|---|---|---|
| without liming | liming | |||||||||
| 30 | 0.958 | 1.75 | 2.05 | 2.89 | 1.91 | 0.950 | 1.85 | 2.48 | 3.01 | 2.07 |
| 60 | 0.967 | 2.08 | 2.18 | 3.04 | 2.07 | 0.981 | 2.05 | 2.70 | 3.18 | 2.23 |
| 90 | 1.02 | 1.96 | 2.25 | 3.15 | 2.09 | 1.00 | 2.14 | 2.84 | 3.20 | 2.30 |
| 120 | 0.985 | 1.90 | 2.38 | 2.90 | 2.03 | 0.963 | 2.09 | 2.65 | 3.11 | 2.20 |
| 360 | 0.966 | 1.90 | 2.09 | 3.15 | 2.03 | 0.940 | 2.13 | 2.90 | 3.05 | 2.26 |
| 420 | 0.945 | 2.25 | 2.20 | 3.26 | 2.16 | 0.971 | 2.41 | 2.78 | 3.17 | 2.33 |
| mean | 0.974 | 1.97 | 2.19 | 3.07 | 2.05 | 0.967 | 2.11 | 2.73 | 3.12 | 2.23 |
| LSD0. 05 for: | A = 0.116 | B = 0.062 | C = 0.159 | |||||||
| A/B = 0.165 | B/A = 0.125 | A/C = n.s. | C/A = n.s. | B/C = n.s. | C/B = n.s. | |||||
Total concentration of copper (mg kg−1) in soil in the incubation experiment
| Days | 0 | 5 % | 10 % | 15 % | Mean | 0 | 5 % | 10 % | 15 % | Mean |
|---|---|---|---|---|---|---|---|---|---|---|
| without liming | liming | |||||||||
| 30 | 1.50 | 3.28 | 3.99 | 5.29 | 3.52 | 1.39 | 3.19 | 3.59 | 4.69 | 3.22 |
| 60 | 2.09 | 3.35 | 3.94 | 5.85 | 3.81 | 2.01 | 3.63 | 4.24 | 5.96 | 3.96 |
| 90 | 2.25 | 3.81 | 6.71 | 5.53 | 3.58 | 2.21 | 5.57 | 4.34 | 5.23 | 4.34 |
| 120 | 2.48 | 3.94 | 5.28 | 6.90 | 4.65 | 2.52 | 4.41 | 5.48 | 5.80 | 4.55 |
| 360 | 1.65 | 4.41 | 4.79 | 6.01 | 4.22 | 1.59 | 3.91 | 4.93 | 5.16 | 3.90 |
| 420 | 1.73 | 3.34 | 4.26 | 5.14 | 3.62 | 1.66 | 3.15 | 4.09 | 5.74 | 3.66 |
| mean | 1.95 | 3.69 | 4.83 | 5.79 | 4.07 | 1.90 | 3.98 | 4.47 | 5.43 | 3.95 |
| LSD0.05 for: | A = 0.183 | B = 0.098 | C = 0.249 | |||||||
| A/B = 0.259 | B/A = 0.197 | A/C = 0.259 | C/A = 0.288 | B/C = 0.241 | C/B = 0.353 | |||||
Fig. 1Percentage share of copper fractions in total content in sewage sludge. F1—easily soluble, F2—exchangeable, F3—bound to MnOx, F4—bound to organic matter, F5—bound to amorphous FeOx, F6—bound to crystalline FeOx, F7—residual
Percentage share of copper fractions in total content in soil in the incubation experiment
| Fertilisation object | F1 | F2 | F3 | F4 | F5 | F6 | F7 | pH |
|---|---|---|---|---|---|---|---|---|
| 30 days | ||||||||
| without liming | ||||||||
| Control object | 2.00 | 1.33 | 0.200 | 34.66 | 19.15 | 16.37 | 26.32 | 4.30 |
| 5 % | 3.35 | 1.83 | 0.183 | 36.59 | 14.11 | 20.58 | 23.35 | 4.55 |
| 10 % | 1.70 | 3.83 | 0.326 | 44.61 | 12.33 | 15.31 | 22.01 | 5.05 |
| 15 % | 5.52 | 4.52 | 0.340 | 40.45 | 13.27 | 13.59 | 22.29 | 5.17 |
| mean | 3.14 | 2.88 | 0.262 | 39.08 | 14.72 | 16.46 | 23.49 | |
| liming | ||||||||
| Control object | 2.88 | 0.216 | 0.288 | 36.76 | 10.94 | 17.55 | 31.46 | 6.30 |
| 5 % | 5.08 | 0.721 | 0.157 | 43.59 | 16.68 | 11.28 | 22.49 | 6.32 |
| 10 % | 2.28 | 4.04 | 0.251 | 45.40 | 13.70 | 12.73 | 21.67 | 6.35 |
| 15 % | 4.50 | 3.22 | 0.265 | 46.27 | 10.92 | 13.37 | 21.49 | 6.48 |
| mean | 3.69 | 2.05 | 0.240 | 43.01 | 13.06 | 13.73 | 24.28 | |
| 60 days | ||||||||
| without liming | ||||||||
| Control object | 1.48 | 1.96 | 0.144 | 26.51 | 34.55 | 9.31 | 26.10 | 4.38 |
| 5 % | 2.70 | 1.73 | 0.149 | 37.40 | 38.01 | 6.90 | 13.13 | 4.80 |
| 10 % | 1.40 | 2.84 | 0.152 | 46.45 | 14.01 | 12.49 | 22.66 | 5.02 |
| 15 % | 3.21 | 2.53 | 0.137 | 48.38 | 11.97 | 10.43 | 23.35 | 5.00 |
| mean | 2.20 | 2.27 | 0.146 | 39.69 | 24.64 | 9.78 | 21.35 | |
| liming | ||||||||
| Control object | 1.69 | 0.746 | 0.099 | 25.62 | 30.80 | 12.14 | 29.00 | 6.25 |
| 5 % | 0.178 | 0.882 | 0.110 | 36.36 | 24.44 | 12.68 | 25.36 | 6.30 |
| 10 % | 1.84 | 2.87 | 0.189 | 37.26 | 20.42 | 11.22 | 26.21 | 6.25 |
| 15 % | 3.31 | 2.10 | 0.101 | 45.69 | 18.39 | 8.28 | 22.13 | 6.50 |
| mean | 1.75 | 1.65 | 0.125 | 36.23 | 23.51 | 11.08 | 25.68 | |
| 90 days | ||||||||
| without liming | ||||||||
| Control object | 1.47 | 1.02 | 0.311 | 28.88 | 26.72 | 13.33 | 28.31 | 4.26 |
| 5 % | 0.656 | 1.26 | 0.210 | 26.81 | 37.17 | 8.95 | 23.95 | 5.15 |
| 10 % | 1.15 | 0.760 | 0.209 | 29.36 | 34.26 | 7.50 | 26.83 | 5.10 |
| 15 % | 3.38 | 1.79 | 0.669 | 38.52 | 38.34 | 9.26 | 8.04 | 5.12 |
| mean | 1.66 | 1.21 | 0.350 | 30.89 | 34.12 | 9.75 | 22.03 | |
| liming | ||||||||
| Control object | 0.181 | 0.407 | 0.226 | 27.00 | 26.08 | 13.08 | 33.10 | 6.25 |
| 5 % | 0.377 | 0.323 | 0.072 | 31.77 | 24.78 | 8.64 | 34.11 | 6.34 |
| 10 % | 1.23 | 0.737 | 0.207 | 36.87 | 38.91 | 10.97 | 10.15 | 6.40 |
| 15 % | 3.17 | 1.11 | 0.201 | 32.89 | 44.36 | 9.45 | 8.81 | 6.45 |
| mean | 1.24 | 0.644 | 0.177 | 32.38 | 33.53 | 10.52 | 21.54 | |
| 120 days | ||||||||
| without liming | ||||||||
| Control object | 0.201 | 0.323 | 0.363 | 24.82 | 23.79 | 11.77 | 41.13 | 4.30 |
| 5 % | 1.65 | 1.57 | 0.381 | 24.44 | 43.65 | 11.24 | 17.06 | 5.17 |
| 10 % | 1.70 | 1.59 | 0.303 | 23.11 | 36.17 | 11.06 | 26.14 | 5.20 |
| 15 % | 3.04 | 1.75 | 0.406 | 32.32 | 41.59 | 9.30 | 11.59 | 5.21 |
| mean | 1.65 | 1.31 | 0.363 | 25.84 | 36.30 | 10.84 | 23.73 | |
| liming | ||||||||
| Control object | 1.09 | 0.238 | 0.317 | 22.22 | 23.41 | 11.51 | 41.27 | 6.31 |
| 5 % | 1.34 | 0.635 | 0.431 | 33.56 | 36.73 | 8.55 | 18.82 | 6.40 |
| 10 % | 1.31 | 1.29 | 0.237 | 30.38 | 36.01 | 6.75 | 24.45 | 6.45 |
| 15 % | 2.74 | 1.59 | 0.293 | 36.38 | 38.79 | 8.83 | 11.38 | 6.37 |
| mean | 1.62 | 0.938 | 0.320 | 30.66 | 33.74 | 8.91 | 23.86 | |
F1—easily soluble, F2—exchangeable, F3—bound to MnOx, F4—bound to organic matter, F5—bound to amorphous FeOx, F6—bound to crystalline FeOx, F7—residual; 5 , 10, and 15 % of sewage sludge to dry mass of soil
Percentage share of copper fractions in total content in soil in the incubation experiment
| Fertilisation objects | F1 | F2 | F3 | F4 | F5 | F6 | F7 | pH |
|---|---|---|---|---|---|---|---|---|
| 360 days | ||||||||
| without liming | ||||||||
| Control object | 0.424 | 0.121 | 0.485 | 31.52 | 39.39 | 17.15 | 10.90 | 4.40 |
| 5 % | 1.22 | 1.63 | 0.181 | 39.23 | 43.31 | 10.52 | 3.91 | 4.80 |
| 10 % | 3.74 | 1.86 | 0.418 | 33.82 | 45.09 | 11.48 | 3.59 | 5.15 |
| 15 % | 3.93 | 2.08 | 0.316 | 40.27 | 39.43 | 11.43 | 2.55 | 5.05 |
| mean | 2.33 | 1.42 | 0.350 | 36.21 | 41.81 | 12.24 | 5.24 | |
| liming | ||||||||
| Control object | 0.252 | 0.377 | 0.189 | 33.08 | 40.00 | 17.92 | 8.18 | 6.10 |
| 5 % | 0.512 | 1.51 | 0.128 | 34.27 | 47.57 | 11.13 | 4.88 | 6.25 |
| 10 % | 1.26 | 1.24 | 0.365 | 40.57 | 42.19 | 10.10 | 4.29 | 6.28 |
| 15 % | 3.04 | 1.71 | 0.271 | 38.37 | 43.60 | 9.17 | 3.84 | 6.35 |
| mean | 1.27 | 1.21 | 0.238 | 36.57 | 43.34 | 12.08 | 5.30 | |
| 420 days | ||||||||
| without liming | ||||||||
| Control object | 0.173 | 0.116 | 0.056 | 30.20 | 36.15 | 23.05 | 10.27 | 4.35 |
| 5 % | 0.479 | 1.26 | 0.240 | 25.16 | 47.90 | 21.58 | 3.40 | 4.90 |
| 10 % | 0.892 | 1.90 | 0.305 | 34.07 | 46.30 | 12.60 | 3.95 | 5.20 |
| 15 % | 1.77 | 2.02 | 0.486 | 34.46 | 45.35 | 13.04 | 2.88 | 5.08 |
| mean | 0.829 | 1.32 | 0.272 | 30.97 | 43.93 | 17.57 | 5.13 | |
| liming | ||||||||
| Control object | 0.181 | 0.060 | 0.181 | 32.05 | 37.35 | 17.53 | 12.65 | 6.00 |
| 5 % | 0.127 | 0.794 | 0.127 | 38.09 | 41.27 | 11.81 | 7.71 | 6.30 |
| 10 % | 0.611 | 1.54 | 0.196 | 31.05 | 50.12 | 11.17 | 5.31 | 6.18 |
| 15 % | 1.27 | 1.60 | 0.331 | 33.97 | 47.21 | 11.52 | 4.09 | 6.28 |
| mean | 0.547 | 0.999 | 0.209 | 33.79 | 44.01 | 13.01 | 7.44 | |
F1—easily soluble, F2—exchangeable, F3—bound to MnOx, F4—bound to organic matter, F5—bound to amorphous FeOx, F6—bound to crystalline FeOx, F7—residual; 5, 10, and 15 % of sewage sludge to dry mass of soil
Simple correlation coefficients between nitrogen, pH and total copper content, and copper fractions in the soil
| N | Cu | pH | ||||
|---|---|---|---|---|---|---|
| −Ca | +Ca | −Ca | +Ca | −Ca | +Ca | |
| F1 | 0.592* | 0.350 | 0.521* | 0.359 | 0.386 | 0.567* |
| F2 | 0.545* | 0.609* | 0.409* | 0.474* | 0.514* | 0.375 |
| F3 | 0.354 | 0.133 | 0.287 | 0.170 | 0.302 | 0.145 |
| F4 | 0.430* | 0.536* | 0.301 | 0.408* | 0.224 | 0.385 |
| F5 | 0.109 | 0.260 | 0.125 | 0.286 | 0.236 | −0.281 |
| F6 | −0.358 | −0.660* | −0525* | −0.717* | −0.433* | −0.676* |
| F7 | −0.427 | −0.513* | −0.255 | −0.448* | −0.371 | 0.166 |
p ≤ 0.05, −Ca—without liming, +Ca—liming, * - significant difference