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Environmental impact from a phosphogypsum storage on soil

Сведения об участнике
ФИО
Каниськин Максим Александрович
ФИО (на английском языке)
Kaniskin Maxim
Название организации
Факультет почвоведения МГУ имени М.В. Ломоносова
Информация о докладе
Вид доклада
Постерный доклад
Секция
Биоиндикация и химический анализ в экологическом мониторинге
Название доклада
Environmental impact from a phosphogypsum storage on soil
Соавторы доклада (ФИО, организация, город, страна)
Аннотация
Проведена оценка биологических и химических показателей алювиальных почв в районе объекта размещения фосфогипса. Выявлено, что в почвах, прилегающих к ОРО наблюдаются повышенные концентрации редкоземельных металлов, в частности Sr, Ba, Ce и La, тогда как концентрации других элементов не превышают установленные ПДК, либо не отличаются достоверно от контрольных значений. Результаты биотестирования почвенных проб с применением червей ( калифорнийских) показал, что почвы, прилегающие к ОРО характеризуются как "остро-токсичные", смертность тест-объектов более 50% относительно контроля. В то время как фитотест на с применением семян горчицы белой не выявил существенных различий между наиболее загрязненными и фоновыми почвами. Результаты оценки ферментативной активности выявили тенденцию снижения активности почвенных каталаз и б-глюкозидазы в почвах, отличающихся повышенными концентрациями загрязняющих веществ по сравнению с контролем.
Ключевые слова
waste, soil, heavy metals, Eisenia fetida, Sinapis alba, enzymes
Введение

Worldwide, a rapid industrialization has consumed vast amounts of various industrial raw materials and larger quantities of industrial solid wastes remained from mining, mineral processing, and smelting processes. Phosphogypsum [PG] is a by-product of the phosphoric acid production and the largest part of them is the disposed by dumping in large stockpiles (storage). Thus, an increasing number of studies have focused on PG assessment and have reported useful information about it chemicals (18) and radionuclides (15) properties. A growing bodies of evidence supported PG for agriculture purposes (20; 22), or using PG as a building material (16;14; 1), but others have reported about damage influence of PG storages on chemical, radiology and ecotoxicology soils properties in different countries (21, 13, 4, 19).

It’s wildly acceptable, that the determination of the pollutants content is not enough to fully evaluate the toxic effects or to characterize contaminated sites because the ecotoxicological danger in the environment is not affected. For a more realistic assessment, we need to compare three blocks of data – chemistry, microbiology and ecotoxicology (9, 6).  In this reason, measuring of the soil extracellular enzymes activity could be helpful, because of their connection with nutrient cycling, and closely link with the physical and chemical dynamics of terrestrial environments (8, 17). As well as, ecotoxicity soil tests like plants (3) and earthworms (2, 7) are wildly determine for the soil samples assessment.

This paper focuses on a triad-based approach applying in parallel different analysis methods. In our triad procedure, we couple a chemical data, with an evaluation of the soil microbiological ecosystem and primary terrestrial biotests. The aims of our study are to (i) reveal the concentration of potential toxic elements in soil around the PG storage, (ii) evaluate the impact of the PG storage on soil health using microbiological indicators such as catalase, acid phosphatase, and β-glucosidase activities, (iii) examine soil ecotoxicology using earthworms Eisenia fetida and plant Sinapis alba.

Методы и материалы

A fluvisol samples were collected i from 6 sites on and in the vicinity of the PG storage to represent the pollution gradient and in a control area (Fig 1). At each site (2x2 m) a soil sample (topsoil layer 0-20 cm depth) was taken by quantization and properly mixed. A portion of the each sample was kept refrigerated (4 °C) at their field moisture to be used in the determination of the soil enzymatic activities. The remaining soil was air dried and sieved to 2 mm for analytical determinations and ecotoxicological evaluation, this part stored for several weeks to several months in cardboard boxes at room temperature.

The total contents of Cu, Zn, Pb, As, Sr, Ba, Ce, Cd and La were determined by digesting with a mixture of HNO3, HF and HClOby ICP-MS (Agilent 7500). Spectrophotometric assays were used to measure the activity of β-glucosidase. Catalase activity was measured by back-titrating residual H2O2 with KMnO4 . Soil ecotoxicity evaluation was performed using terrestrial tests to assess the improvement in soil 'habitat function' and comprised the E. fetida mortality and phytotoxicity.

Statistical differences between polluted samples and control were analyzed by a one-way analysis of variance (ANOVA) followed by the separation of the treatments from controls, by applying post-hot Tukey-Kramer HSD (P ≤ 0.05) tests. All statistical analyses were performed using Statistica12 Statsoft©.

Полученные результаты

The PG at this storage was acidic in pH with a mean value of 2.36, major element analysis shows that it rich with a 29.8% CaO, 0.16% Na2O, 0.013% Fe2O3, 19.2% SrO, 0.24% F, 0.78% P2O5, 45.3% S (in the form of SO3). A remarkable feature of this PG is the extremely high degree of rare elements La and Ce, higher than that of the samples of PG from Togo and Idaho sources (18) and particular the same as in the PG from Cubatão region, southern Brazil. 

In the present work, the relatively high pHH2O of the soil is detected, also a significant increasing of potentially toxic elements contents in soils near the PG storage is observed (Table 1). An average concentration of sulfates was extremely high - 3123 mg/kg of soil, and exceeded by 27 times the local background value (117 mg/kg), the same as the average concentration of fluoride and calcium in soils near the storage. An average concentration of sulfates was extremely high - 3123 mg/kg of soil, and exceeded by 27 times the local background value (117 mg/kg), the same as the average concentration of fluoride and calcium in soils near the storage. According to the previous results Marques et al. (5) and Martínez-Sánchez et al. (11), we expected a multi-component pollution in soil, predominantly high concentration of Cu, Cd, Co, Ni, Pb and As. Our results reveal prevalence of La, Ba, Ce and Sr pollution in soil near the storage, while the concentration of Cu, Zn, Pb and As were in the permitted levels.

Table 1. Analytical parameters and chemical characteristics of soil samples (Mean ± SD, n=4). Different letters represent significant differences between samples on rows according to the Tukey-Kramer HSD test (p ≤ 0.05).

Parameters

The storage edge

Near the river

 Control

P1

P2

P3

P4

P5

P6

P7

pH(H2O)

7.4 ± 1.5a

7.6 ± 1.5a

8.0 ± 1.6a

7.6 ± 1.5a

7.8 ± 1.5a

5.8 ± 1.2a

7.2 ± 1.4a

CE (dScm−1)

1.94 ± 0.38ab

1.98 ± 0.39ab

2.41 ± 0.48a

0.8 ± 0.16bc

0.82 ± 0.16bc

1.02 ± 0.2ac

0.32 ± 0.06c

Total concentration, mg kg-1

Cu

52.0 ± 3.2bc

88.5 ± 11a

16 ± 4d

24.1 ± 5.1cd

50.4 ± 6.1bc

64.9 ± 5ab

29.7 ± 3.11cd

Zn

83.8 ± 20.95a

110.7 ± 27.68a

43.8 ± 10.95a

69.1 ± 17.28a

106 ± 26.5a

144.5 ± 36.13a

124.5 ± 31.13a

Pb

36.9 ± 5.54b

74.9 ± 11.24a

10.89 ± 1.63b

15.9 ± 2.39b

36.7 ± 5.51b

35.4 ± 5.31b

23.45 ± 3.52b

As

39.9 ± 5.99a

46.7 ± 7.01a

43.1 ± 6.47a

23.3 ± 3.5a

30.7 ± 4.61a

48.2 ± 7.23a

29.7 ± 4.46a

Sr

2517 ± 567.11a

2331 ± 125.5a

792 ± 202.8b

118.6 ± 10.18b

198.6 ± 22.1b

469.3 ± 65b

81.6 ± 5.7b

Ba

297.8 ± 11.8a

210.5 ± 25.87bc

245.2 ± 14.4ab

273.3 ± 15.2ab

156.2 ± 15.2cd

117.4 ± 13.5de

71.2 ± 5.8e

Ce

121.1 ± 21.11a

140.5 ± 11.81a

57.7 ± 10.25b

30.2 ± 4.02b

21.3 ± 5.11b

44.1 ± 3.3b

33.3 ± 3.01b

La

72.5 ± 5.7a

60.1 ± 3.4ab

34.6 ± 10.1bc

38.4 ± 5.2bc

15 ± 3.8c

11.1 ± 4.1c

14.8 ± 5c

The two acute toxicity tests on soil (earthworm and plant) did not exhibit the same sensitivity. While the E. fetida test reveals a pronounced toxicity in soil samples collected near the storage, S. alba test undistinguished significant response at the gradient of concentration (fig. 2). Sinapis alba roots length elongation in control have the same measures like in the samples, collected near the storage. This evaluate could be explained by several points (i) the high concentration of P and Ca in the soil samples could obscure the toxicity effect of heavy metals by growth promoting (11); (ii) the enzymatic antioxidation capacity could be the predominantly mechanism in tolerance of seeds to PG amendments as it was shown for sunflowers seeds by Elloumi et al (10). The same tendency regarding the sensitivity of earthworms E. andrei and non-sensitivity plants Z. mays and L. sativa (12), and the opposite very high toxicity to L. sativum and S. alba (11) have been previously reported for PG contaminated and amendment soils.

The response of catalase, and β-glucosidase are shown in Fig. 3. The highest recorded catalase activity was at the value of 2.33 ± 0.12 (μg O2 g−1 dry soil min-1) in the control sample. Reduction of catalase activity as a consequence of PG storage was stronger in P1, P2 and P4 samples, than in the P3 and P6. The same tendency is detected for β-glucosidase activity.

 

Заключение

The main purpose of this investigation was to assess the PG storage influence on surrounding land not only with chemical methods but with a complex approach includes bioassay and enzymes activity measure. The prevailed pollution in the environment surrounding the storage were rare elements, especially Sr and La. The ecotoxicology effects of earthworm E. fetida by the polluted soils were particularly remarkable and confirmed that the applied bioassay with invertebrates may be used to determine the potential risk in a determinate area where PG is presented. 

Цитируемая литература
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Благодарности
The reported study has been financed by Russian Found of Basic Research (RFBR) according to the research project No.16-34-00063 mol_a.
Название, авторы, резюме (на английском языке)

This paper focuses on the integral soil screening approach using chemicals, ecotoxicology, and molecular microbiology methods to developing an environmental risk assessment by storage of phosphogypsum [PG]. Soil samples were collected on and in the vicinity of the existing PG storage, Russia.

The analysis of potentially toxic elements highlights exceeded levels of pseudo-total values for La, Ba, Ce and Sr, and elevated levels of soluble forms of F-, Ca2+ and sulfates. Other chemical metrics for pH(KCl), and pseudo-total concentration of As, Cu, Cd, Ni and Zn are insignificant from the reference soil.

The ecotoxicology data suggest that acute tests with earthworms E. fetida (ISO 11268-1 2012) and plants S. alba (Phytotoxkit 2004) do not exhibit the equal sensitivity to PG polluted soils. While the E. fetida test reveals a pronounced toxicity in polluted samples, S. alba test does not detect any significant response. Stepwise regression analysis showed Sr, La, Ce and Ca, sulfates to be the dominant factors determining the influence of earthworms.