ISSN 01476874, Moscow University Soil Science Bulletin, 2012, Vol. 67, No. 1, pp. 33–38. © Allerton Press, Inc., 2012. Original Russian Text © A.I. Shcheglov, O.B. Tsvetnova, 2012, published in Vestnik Moskovskogo Universiteta. Pochvovedenie, 2012, No. 1, pp. 37–42.

Content of Some Organic and Inorganic Pollutants in Soils of Southern Part of Sakhalin Island A. I. Shcheglov and O. B. Tsvetnova Moscow State University, Moscow, Russia email: [email protected], [email protected], [email protected] Received May 31, 2011

Abstract—The article is dedicated to analyzing the content and distribution of oil hydrocarbons, benz(a)pyrene, and heavy metals in the soils of the southern part of Sakhalin Island. The investigations were conducted in 2003–2010. A dynamical increase in the content of ecotoxicants in soils has been shown. The similar character of the accumulation of oil hydrocarbons, benz(a)pyrene, and heavy metals in the soils has been determined and indicates the possibility of the aerial transmission of pollutants from existing nearby sources. Keywords: soils, southern part of Sakhalin Island, pollution, oil hydrocarbons, benz(a)pyrene, heavy metals. DOI: 10.3103/S0147687412010073

INTRODUCTION

soils of Sakhalin is 15 (southern part of the island) and 50 (northern part) mg/kg on average. It should be noted that there are natural anomalies in the field where PHC is output to the surface and there is a considerable range of variations (max–min) in the considered parameters [12]. However, data on the background characteristics of the content of organic and inorganic toxicants in the soils of Sakhalin are disjointed and not fully characterized. There are indications that the average total content of copper in soils of the island ranges from 10 to 60 and mobile forms of this element are 4.5–8.2 mg/kg of soil [16]; for zinc, these figures are <30 and 0.9–2.6 mg/kg soil, respectively [4, 5]. The levels of background concentrations of other trace elements can only be judged by the results of studies of noncontaminated soils of Primorye. In particular, the total content of nickel is 45 mg/kg of soil on average [2] and there is an increased amount of cadmium and arsenic, which reflects the regional characteristics of soils in the Far East. Fur thermore, data on the background concentrations of benzo(a)pyrene (BP) in the soils of the investigated region are scarce. There are indications that, in the soils of Kamchatka and the Kuril Islands, these figures vary from 0.3 to 14.6 µg/kg [17]. At the same time, elevated levels of BP are most likely due to volcanic activity, which is one of the nat ural sources of polycyclic aromatic hydrocarbons in the biosphere, including benzo(a)pyrene (C20H12) [8]. In this regard, the objective of this work is to assess the current levels of petroleum hydrocarbons, benzo (a)pyrene, and some heavy metals in the soils of the southern part of Sakhalin Island.

Sakhalin Island is Russia’s oldest oilproducing region, as this industry has been developed there since the 1920s. At present, onshore and offshore the Okhotsk Sea, there are 69 open hydrocarbon deposits (oil, gas, gas condensate, gas and oil, oil and gas, and oil and gas condensate) [10]. A number of large and small oil and gas pipelines intersect in different direc tions on the island, where they are put into operation at an oil refinery, Onshore Processing Facilities (OPF), a gas liquefaction plant with an oilexport ter minal (LNG/OET), etc. All of this greatly enhances the technogenic impact on the components of the environment, including soil cover, which causes the development of degradation processes and increase the degree of soil contamina tion. Obviously, in this case, the priority pollutants will be mineral oil, polycyclic aromatic hydrocarbons, and heavy metals (HMs). In the initial period of the development of hydro carbon fields, pressure associated with extraction and refining was observed to the greatest extent on the northern part of the island; however, the operation of the LNG/OET plant1 has led to increasing anthropo genic pressure on the southern part of Sakhalin. According to the available literature sources, depending on the geochemical landscape conditions, the petroleum hydrocarbon (PHC) background in the 1 The

LNG/OET plant is located on the coast of Aniva Bay near Prigorodnoe village, 13 km from Korsakov and 53 km from YuzhnoSakhalinsk. Construction was begun in 2003 and exploitation was begun in 2009.)

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Table 1. Content of some ecotoxicants in 0–20cm layer of brown forest unsaturated acid soils of the southern part of Sakhalin Island (according to 2003 data) Organic pollutants, mg/kg Inorganic pollutants, mg/kg petroleum benz(a)pyrene hydrocarbons 71.0

0.06

Pb

Zn

13.7

39.7

Hg

Cd

0.085 0.045

Table 2. Statistical indicators of PHC content in soils (according to 2010 data when n = 12) Upper organ ogenic strata (litter, mat)

Underlying strata to the depth 20 cm

1567.47

283.99

286.81

142.34

Maximum value, mg/kg

4020.69

1737.74

Minimum value, mg/kg

403.81

52.76

Standard deviation

993.53

493.09

63.4

173.6

Indicator Average value, mg/kg SEM, mg/kg

Coefficient of variation, %

MATERIALS AND METHODS Experiments were carried out in dynamics in 2003–2010 in the southern part of Sakhalin Island on the territory covering the area potentially effected by the oil and gas industry, including LNG/OET. This ter ritory contains test sites (TSs) with areas of 50 × 50 m PHC content mg/kg 2500

1

2

2000 1500 1000 500 0

Bog lowland

Brown forest acidic

Brown forest podzolic

Upland brown forest

Fig. 1. Average PHC content in 0–20cm layer of soils of southern part of Sakhalin Island: (1) upper organogenic strata (litter, mat); (2) underlying strata to depth of 20 cm.

with a characteristic and undisturbed soil cover. TSs cover the main types of soils in the region and were located at different distances from possible sources of contamination. At each TS, we established anchor sections, from which samples were taken layer by layer according to genetic horizons in order to characterize the basic physical and chemical properties of soils formed here, as well as to assess the levels of petroleum hydrocar bons, benzo(a)pyrene, and heavy metals (Cd, Cu, Hg, Pb, Ni, Zn, Cr). In the prepared soil samples, we determined the total content of petroleum hydrocarbons by infrared spectroscopy (standard method [11]), the concentra tion of benzo(a)pyrene by chromato mass spectrome try [19], and acidsoluble (1n. HNO3) compounds of heavy metals by the atomic adsorption method in flame mode [15]. RESULTS AND DISCUSSION Studies have shown that, in the southern part of Sakhalin Island, there are various subtypes of brown forest soils in the area where there are a number of alluvial soils of marsh; mountain soils are confined to the tops of mountains and ridges [1, 3, 4, 6]. As a rule, they have a very strongly acidic reaction of the medium, are not saturated with bases, and are char acterized by high variation of the organic matter content (loss on ignition is 2.5–90%), which prede termines the high heterogeneity of the accumulating capacity of organogenic horizons and the intensity of the migration of various ecotoxicants in their pro files. At the initial stage of research in the southern part of Sakhalin Island (2003), levels of PHC, BP and a number of heavy metals in soils generally differed only slightly from the values previously established for the background areas of the region and mentioned above [2, 4, 5, 12, 16, 17] (Table 1). Thus, according to the baseline, the levels of ecotoxicants in soils were in the range of the back ground values. It is obvious that in this period of anthropogenic impact on soils of the territory was minimal. However, according to the data 2010, the average levels PHC, as well as variation of this indica tor in soils of the southern part of Sakhalin Island increased, especially in the upper organogenic hori zons (Table 2). It should be emphasized that the maximum levels of PHC accumulation are observed in the surface hori zons (litter) of brown forest soils and in the marshy lowland peaty gley soils of the underlying mountains mat T1 (Fig. 1). In the underlying bedding strata of brown forest soils, the NUV content decreases sharply to 40– 60 mg/kg, while in the corresponding peatbog fen peat thickgley soils, it remains at a fairly high level,

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CONTENT OF SOME ORGANIC AND INORGANIC POLLUTANTS PHC content mg/kg 2500 Brown forest 2000 1

2

3

1500 1000 500 0

O A/AlA2 AB/A2B B1

B2

BC

35

PHC content mg/kg 1400 Bog lowland 1200 1000 800 600 400 200

C

Mat

T1

T2

Tg

G

Fig. 2. PHC distribution in profile of brown forest bog lowland peaty gley soils: (1) brown forest acidic unsaturated, (2) brown forest acidic podzolic, (3) upland brown forest.

i.e., around 800 mg/kg; only in the gley horizon does this figure drop to 400 mg/kg (Fig. 2). Thus, the increased concentration of PHC is observed in organic soils and horizons. In general, according to the accepted gradations based on the levels of PHC con tent in soils, the studied area can now be classified as having a level of contamination from 2 (low) to 4 (high) [9, 11, 13]. A content analysis of BP in the 0–20 cm layer of soil showed that, according to the 2010 data, the con centration of this compound ranges from 0.0001 to 0.0084 mg/kg of soil at the highest rates in the surface organic horizons (Table 3). However, unlike the latter, in all cases, the highest levels of BP accumulation are observed in the surface horizons and, in a number of investigated soils, in marshy lowland peaty gley soil (Fig. 3). That is the maximum concentration recorded in BP levels, which are most affected by anthropogenic emissions and in soils that are the nearfield effects of the LNG/OET. In the soil profile, the BP content drops sharply to trace amounts with increasing depth. In this case, unlike the PHC, profile changes in the content of this compound in organogenic and mineral soils are of the same type (Fig. 4). Under current regulations, the BP content in the soil of investigated area can be classified as having a low level of pollution [14]; in other words, com pared to the PHC, BP is expressed in a much lower degree. An analysis of the content of inorganic pollutants (heavy metals) in the soils of the southern part of Sakhalin Island has shown that significant differences compared to their background concentrations are not observed (Table 4). For almost all acidsoluble com pounds of investigated heavy metals, an excess of MAC is not observed [14], except for zinc. The zinc content (30 mg/kg) in the surface organic layer char acterizes the average level of pollution; however, we emphasize that it can be seen as the result of regional MOSCOW UNIVERSITY SOIL SCIENCE BULLETIN

features of the content of this element in soils of Sakhalin Island [4, 5]. For the majority of heavy metals (zinc, lead, mer cury, cadmium), the maximum concentrations of their acidsoluble compounds, as well as the afore mentioned organic pollutants, are observed in the upper organogenic horizons (litter, mat), while for others (copper, chromium), the maximum concen trations are observed in the lower layers soil stratum (Table 4). Increased heavymetal concentrations on the surfaces of organic soil horizons, in particular zinc, which is of great importance in plant physiology, as well as lead, mercury, and cadmium, the necessity of which for plants has been challenged [7, 18], may be due to their airborne entrance into the environment from existing sources of pollution. The accumula tion of a number of heavy metals in the illuvial hori zon as a result of removal from the overlying strata PHC content mg/kg 0.006

1

2

0.005 0.004 0.003 0.002 0.001 0

Bog lowland

Brown forest acidic

Brown forest podzolic

Upland brown forest

Fig. 3. Average BP content in 0–20cm layer of soils of southern part of Sakhalin Island: (1) upper organogenic strata (litter, mat); (2) underlying strata to depth of 20 cm. Vol. 67

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SHCHEGLOV, TSVETNOVA PHC content mg/kg 0.006 Bog lowland

PHC content mg/kg 0.006 Brown forest 0.005 1 2 0.004 0.003 0.002 0.001 0 O A/AlA2 AB/A2B B1

B2

0.005 3

0.004 0.003 0.002 0.001

BC

0

C

Mat

T1

T2

Tg

G

Fig. 4. BP distribution in the profile of the brown forest bog lowland peaty gley soils: (1) brown forest acidic unsaturated, (2) brown forest acidic podzolic, (3) upland brown forest.

Bog lowland soils

25

40 35 30 25 20 15 10 5 0

Heavymetal concentration, mg/kg

20 15 10 5 0 35 30 25 20 15 10 5 0

Mat

T1

T2

Tg

G

Upland brown forest soils

30

Brown forest acidic podzolic soils

O A1A2 A2B Blm B2g BCg

C

Brown forest acidic unsaturated soils

25 20 15 10 5 O

A

AB Blm B2

BC

Cr

Cu

Ni

0

C Zn

O

A1

AB

Cd

Hg

Pb

Blm

Fig. 5. Distribution of acidsoluble compounds of heavy metals in profiles of studied soils.

can be traced in the underlying strata of the investi gated soils, including in the composition of fine par ticles [7]. This is especially true for brown forest acid soils. Table 3. Statistical indicators of the BP content in soils (according to 2010 data when n = 12) Indicator

Upper organ ogenic strata (litter, mat)

Underlying strata to the depth 20 cm

Average value, mg/kg SEM, mg/kg Maximum value, mg/kg Minimum value, mg/kg Standard deviation Coefficient of variation, %

0.0044 0.0006 0.0084 0.002 0.0019 44.4

0.00043 0.0002 0.0026 0.0001 0.0007 167.7

Depending on the chemical nature of the elements, their mobility and impact on them the major soil forming processes, the distribution of TM in soils has different types of distribution (Fig. 5): cadmium has accumulation distribution, zinc and lead have accu mulation–eluvial–illuvial distribution, and copper and chromium have eluvial–illuvial distribution. As a result, we can state that, compared to the initial period of research in studied heavymetal soils, there is no evident contamination; however, increased accumula tion in the soil of an cidsoluble compound of lead and cadmium in the surface organic layers of litter and mat may be indicative of the increasing aerial influx of these elements in the natural environments of the southern parts of Sakhalin Island. To some extent this may apply to zin; however, as outlined above, that may be due to regional characteristics of the investigated soils [4, 5].

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Table 4. Statistical indicators of acidsoluble heavymetal content in soils (when n = 12) Element

Depth

Cd

1 2 1 2 1 2 1 2 1 2 1 2 1 2

Cu Pb Ni Zn Cr Hg

Average value, Maximum Minimum SEM, mg/kg mg/kg value, mg/kg value, mg/kg 0.24 0.17 0.64 1.12 4.79 2.20 0.74 0.61 30.68 5.23 1.42 2.29 0.033 0.009

0.01 0.05 0.06 0.41 0.48 0.36 0.10 0.26 2.20 1.27 0.17 0.61 0.005 0.002

0.32 0.54 0.87 4.75 7.70 5.77 1.24 3.38 40.28 12.64 1.96 8.21 0.069 0.032

0.15 0.013 0.12 0.24 2.11 0.92 0.13 0.15 17.04 0.25 0.34 0.78 0.007 0.003

Standard deviation

Coefficient of variation, %

0.05 0.19 0.20 0.41 1.65 1.25 0.35 0.90 7.60 4.39 0.59 2.10 0.016 0.008

20.6 112.3 37.6 126.0 34.5 57.0 46.9 148.6 24.8 84.0 41.5 91.5 49.4 87.8

Note: 1—upper organogenic strata (litter, mat); 2—underlying strata to depth of 20 cm.

CONCLUSIONS An analysis of changes in the PHC content and dis tribution, BP, and acidsoluble heavymetal com pounds indicates an increase in the concentration of these ecotoxicants in soils of areas of the southern part of Sakhalin Island. The distribution of PHC, BP, and heavy metals in the profile of the studied soils is similar in nature, they accumulate in the surface organic hori zons, which indicates the possibility of aerial income of these pollutants in the natural environments in the observed area from one or more sources of pollution. These sources can be vehicles, the traffic intensity of which in the studied area increased significantly with the beginning of construction of the petroleum province, as well as objects for exploiting the petro leum province, in particular the LNG/OET plant. The acid–base properties of the soils environmen tally formed here are characterized as negative, so aerial flows of pollutants can lead to a substantial increase in the intensity of their migration in the soil– plant and soil–subsoil waters systems. REFERENCES 1. Bogatyrev, K.P., Ivlev, A.M., and Rudneva, E.I., On Sakhalin Mountain Soils, in Trudy Sakhalinskogo kompleksnogo NII (Scientific Works of Sakhalin Com plex Scientific Research Institute), YuzhnoSakha linsk, 1990, no. 9. 2. Golov, V.I., Microelements Content in Basic Soil of Primorye Plain and the Amur River Region, in Genezis burykh lesnykh pochv (Genesis of Brown Forest Soils), Vladivostok, 1972. MOSCOW UNIVERSITY SOIL SCIENCE BULLETIN

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