State Enterprise “L.I. Medved’s Research Center of Preventive Toxicology, Food and Chemical Safety, Ministry of Health of Ukraine”, Kyiv, Ukraine

Abstract. Recently, the problem of environmental safety through the formation of large volumes of waste has become of particular importance. Activities in the field of production and consumption waste management are one of the most environmentally hazardous and cause significant anthropogenic action due to the risk of adverse effects of hazardous chemical and biological compounds — the constituents of waste products for human health and environment. Any waste, especially in violation of the rules of handling may become environmentally hazardous at certain conditions.
Objective. To determine the influence of solid household waste landfills in the Region of Kyiv on adjacent environmental objects (atmospheric air, soil, soil and surface waters).
Methods. Sanitary chemical, organoleptic, physical and chemical.
Results. The results of experimental studies of the environmental objects at the places of solid household waste landfills suggest the pollution of atmospheric air with formaldehyde, surface and ground waters, soils with hazardous chemical compounds — petroleum products, phenol, heavy metals, ammonium nitrogen, nitrates.
Conclusion. Obtained experimental data indicate the discrepancy of the data of solid household waste landfills with regulatory documents regulating the arrangement and functioning of such landfills, and their operation takes place with violation of environmental requirements.
Key words: solid household waste landfills, EU Directive, Ukrainian legislation, heavy metals.

Unlike European countries, there is a la¬rge number of solid household waste landfills (SHW) in Ukraine. This is due to the fact that in Ukraine, this is the most widespread and cheapest way to dispose of SHW at specially equipped landfills or even in unauthorised dumps. This is associated with a range of factors: lack of state devel¬oped infrastructure in the field of han¬dling (sorting, processing) of solid household waste; with low cost of construction of landfills (in comparison with European standards under observance of all norms and requirements); with low tariffs for the placement of SHW (which is a disintegrator to reduce the amount of waste to land¬fills); with a low level of control over the compliance with environ¬mental legislation (which all¬ows the existence of dump landfills, which do not meet any environmental safety standards) [1].

In places of accumulation of waste at landfills, there is a constant range of hazardous chemicals – nitrogen oxides, sulphur oxides, acetic acid, acetic aldehyde, ammonia, hydrogen sulphide, formaldehyde. Depending on the physical and biological characteristics, reactions that lead to the formation of methane, carbon dioxide, unpleasant odour and filtrate may occur at the dumps. Products of transformation as a result of such factors as high temperatures (fire), as a result of synthesis and thermal decomposition, may form phosgene, hydrogen sulphide, nitrogen oxides, hydrocyanic acid, polychlorinated dibenzo-p-dioxins and dibenzofurans.

Since the disposal technology at landfills is often violated (untimely overlapping of waste mass with the insulating material), there is a constant release of methane and filtrate. Filtration water from sedimentation tanks is the source of volatile components into the atmosphere, which is accompanied by a negative impact on the natural environment. Waste from polymeric materials is a constant factor of the human living environment. Given their wide scope of application and limited lifetime, they account for a significant amount of waste. Disposal is not accompanied by biological decomposition, therefore, the destruction of polymeric materials with the release of hazardous chemicals (formaldehyde, phenol, styrene, benzene, ethylbenzene, methanol, acetone, dimethylamine, toluene, butyl phthalate, dioctyl phthalate, caprolactam) takes place. Given that the polymeric materials are dielectrics, the likelihood of the appearance of electrostatic discharge and ignition/self-ignition on the household waste landfills increases. Their burning, especially of PVC materials, may be accompanied by the release of such extremely hazardous substances as dioxins into the air [2].

Currently, the classic way of waste disposal (container – garbage truck – dump – reclamation) is inefficient and, moreover, potentially dangerous, because even a carefully treated and soil-covered dump is the source of “landfill gas” that stimulates the greenhouse effect. Wastes can be factors that stimulate a negative impact on climate change, human. Since the territory of storage and disposal of SHW belong to objects of high sanitary danger due to its impact on the environment and population. Currently, the problem of recycling and disposal of waste is one of the priority tasks. The stable waste management system in Ukraine has not been settled, there are no means and methods for sorting and recycling garbage. Every day thousands of tons of garbage are taken to the dumps, and the state of dumps often does not meet sanitary standards. The utilisation of existing dumps for SHW and other wastes in Ukraine takes place with violation of environmental requirements, and almost 90 % of waste dumps do not comply with environmental safety. Inappropriate reclamation of waste dumps is carried out, and only 20 % of those requiring reclamation are covered by relevant works [3].

At the same time, the requirements of the Waste Disposal Directive 1999/31/EC (Council Directive 1999/31/EC as of April 26, 1999, on waste disposal as amended by Regulation (EC) 1882/2003) include eight basic provisions [4]:

1.    Development and adoption of national legislation.
2.    Set out the classification of waste disposal sites.
3.    Preparation of a national strategy for reducing the amount of biodegradable waste directed to landfills.
4.    Set out a system of procedures for applications and issuing permits, as well as procedures for taking waste at landfills.
5.    Set out control and monitoring procedures during operation and closure of landfills, as well as after-care procedures after closing.
6.    Implementation of plans to fit existing disposal sites.
7.    Set out a mechanism for calculating the cost of waste disposal at the landfill.
8.    Ensuring the necessary treatment of the relevant waste prior to their disposal.

These provisions prohibit disposal of untreated waste at the landfills. Currently, such a requirement has been fixed in Ukraine at the legislative level since 2018. However, considering the pace of development of SHW management infrastructure, the need to introduce additional means and incentives should be raised. Otherwise, the specified legislation standard will become one of the standards that will not be implemented in practice [5, 6].

Objective. Determine the influence of solid household waste landfills on environmental objects — atmospheric air, soil, ground waters, and natural reservoirs.

Materials and methods. The study was carried out at the environmental objects (surface and ground water, soil, air) near SHW landfill No. 5, Village of Pidhirtsi, District of Obukhiv, Region of Kyiv and SHF landfill near the Village of Kriukivshchyna, District of Kyievo-Sviatoshyn, Region of Kyiv.

Organoleptic, sanitary-chemical, physicochemical methods of study were used. The intensity of odour was determined by a five-point scale (Wright R. H., 1966, DSTU EN 1420-1: 2004). Quality of water. Determination of the influence of organic substances on the quality of water intended for human consumption. Assessment of water in pipeline systems by odour. – Part 1. Test method (EN 1420-1:1999, IDT). Determination of the content of nitrates, chlorides, sulphates was carried out by A. P. Kreshkov. “Basis of analytical chemistry”, vol. 1, 4th edition “Chemistry”, M 1976; petrochemicals – according to “CMEA. Unified methods for water quality studies. Part 1 – Methods of chemical analysis of waters”; ammonium nitrogen — in accordance with the CRD 211.1.4.030-95; phosphates — according to Yu. Yu. Lurie procedure “Analytical chemistry of industrial wastewater”, Moscow, “Chemistry”, 1984; determination of BOC5 was carried out in accordance with the CRD 211.1.4.024-95, determination of the COC — in accordance with CRD 211.1.4.020-95. The level of heavy metals — by the method of atomic emission spectrometry with inductively coupled plasma according to DSTU ISO 11885: 2005 “Quality of water. Determination of 33 elements by inductively coupled plasma atomic emission spectrometry” (ISO 11885: 1996, IDT). Formaldehyde — by the method of reaction gas-liquid chromatography with 2,4-dinitrophenylhydrazine (Certificate No. 77-90 GOSSDME as of June 19, 1990 State Standard of the USSR//Determination of the content of hazardous substances in the air — by gas-liquid chromatography; Procedures of the GOSSMME of the State Standard of the USSR, Moscow, 1991); phenol — by gas-liquid chromatography (Certificate No. 76-90 of the GOSSDME as of June 19, 1990). State Service of the State Standard of the USSR. Determination of the content of hazardous substances in the air — by gas-liquid chromatography; Procedures of the GOSSDME of the State Standard of the USSR, Moscow, 1991). Determination of suspended substances — in accordance with the “Procedure of gravimetric determination of suspended substances in natural and waste waters”, CRD 211.1.1.039-95, approved by the Ministry of Environmental Protection and Nuclear Safety of Ukraine, April 25, 1995. Determination of volatile and limited volatile organic compounds was carried out by elution of adsorbed on solid-phase sorption cartridges of components with acetonitrile (HPLC grade). Subsequently, the study of the eluates was carried out by gas chromatographic mass spectrometry. The chromatographic separation of samples was performed on a Focus GC gas chromatograph with a DSQ mass-selective detector (Thermo Scientific). Chromatographic column DB-5 x 30 m x 0.25 mm x 0.25 µm. The components were detected on a quadrupole mass spectrometer (ionisation type – electron impact – EI – under electron energy of 70 eV). Scanning of positive ions, m7Z, was carried out in the range of 50–400 Dalton. Identification of the detected substances was carried out by comparing the experimental mass spectra of the components with the standard library base of mass spectrometric data (about 200,000 mass spectra). NIST MS Search v.2.0, 1998. The US National Institute for Standards and Technology (NIST USA). Reliable identification was considered for the coincidence of experimental mass spectra of components with a standard library base of mass spectrometric data of more than 70 %. The analysis of the results was performed by matching the sample chromatograms and the control sample.

Results and discussion. Six samples of water from wells, four samples of water from natural reservoirs, three samples of soil for the content of heavy metals, petroleum products, phosphates, nitrates, ammonium nitrogen, formaldehyde, phenol, surface-active ingredients, BOC5, COC were studied; one sample of atmospheric air was studied for the content of formaldehyde and volatile organic compounds.

Results of organoleptic studies of water samples from wells of the Village of Kriukivshchyna (samples No. 1–5) and Village of Pidhirtsi (No. 6) suggest that all samples of water were transparent, colourless, without precipitate, pH 6.5–8.5, odour intensity was not more than 1 point corresponding to the requirements of DSanPiN 2.2.4-171-10 “Hygienic requirements for drinking water intended for consumption by human”. Results of sanitary-chemical studies are provided in Table 1.

Table 1. Results of sanitary-chemical studies of water samples from wells of the Village of Kriukivshchyna (Nos. 1–5) and Village of Pidhirtsi (No. 6).

Notes:
1. for piped water.
2. for water from shafts (DSanPiN 2.2.4-171-10 “Hygienic requirements for drinking water intended for consumption by human”).

The analysis of the obtained study results shows that in the samples of water taken from wells of the Village of Kriukivshchyna, nickel contamination was detected (exceeding the hygienic rate 7.5-fold in one sample out of 5), petroleum products (exceeding the hygienic rate 1.2–22.5-fold in four samples out of 5), ammonium nitrogen (exceeding the hygienic rate 5.9–55.8-fold in all 5 samples), nitrates (exceeding the hygienic rate 2.3–2.7-fold in 2 samples out of 5). In the sample of water taken from the well of the Village of Pidhirtsi, 2-fold excess cadmium levels were detected, and mercury was 11 times higher. Existing regulatory documents (DSanPiN 2.2.4-171-10 “Hygienic requirements for drinking water intended for consumption by human”) do not require control for the content of heavy metals and petrochemicals for water of shafts and wells.

Water extracts (1:10) were prepared, incubated for 24 hours at 40 °C with constant stirring for sanitary-chemical studies of soil samples. Extracts were transparent, colourless, odourless, pH 5.5–7.6. Study results are provided in Table 2.

Table 2. Study results of the soil samples.

Notes:
1. EPA (The US Environmental Protection Agency, USA).
2. Dutch Target and Intervention Values, 2000 (The New Dutch List, the Netherlands)
3. Odour intensity is determined by a five-point scale (Write R. H., 1996)

Study results of the soil sample No. 1 (Village of Kriukivshchyna) suggest that metal levels meet the hygiene standards established in the US and EU. Soil sample No. 2 (near SHW No. 5), there is a 14.6-fold excess of arsenic (US standards). A slight increase in lead content (the US and EU standards) was registered in the soil sample No. 3 (near SHW No. 5), a 20-fold excess of arsenic content (US standards), and 2-fold excess in cadmium (EU standards) were detected.

The sanitary-chemical studies of water samples from natural reservoirs near the landfills were carried out, and results are presented in Table 3.

Table 3. Results of sanitary-chemical studies of water samples from natural reservoirs.

Notes:
1. Decree of Kyiv City State Administration No. 1879 as of October 12, 2011 “On Approval of the Rules for Reception of Waste Water of Enterprises into the Sewage System of Kyiv” 
2. Decree of the Cabinet of Ministers of Ukraine No. 465 as of March 24, 1999. “On Approval of the Rules of Surface Water Protection from Pollution with Return Water”.
3. Dutch Target and Intervention Values, 2000 (The New Dutch List, the Netherlands)

The results of the conducted studies suggest that in the sample of water from the lake Kriuchok (near the Village of Kriukivshchuna), a slight excess of the level of ammonium nitrogen (Ukrainian standards), cadmium (EU standards), as well as a 12-fold excess of petrochemicals (EU standards) was detected. Water from this reservoir does not meet the domestic requirements by the parameters of BOC5 and COC. In a sample from the lake Kupel (near the Village of Kriukivshchyna), excessive levels of such hazardous chemicals as petrochemicals — 8-fold, cadmium — 150-fold (EU standards) was detected. Water from the lakes Kriuchok and Kupel does not meet the domestic hygienic rates by the parameter of “suspended substances”.

The results of the conducted studies suggest that in samples of water from the river Siverky (near SHW landfill No. 5), 10– a 250-fold excess of phenol level (EU standards), a 9.3-fold excess of the content of nitrates (Ukrainian standards) was detected.

Studies were conducted to determine the content of hazardous chemicals in the atmospheric air in the Village of Pidhirtsi near SHW landfill No. 5. Study results indicate that the level of formaldehyde is exceeded 1.33-fold compared with the established hygienic rates (“Maximum permissible concentrations of chemical and biological substances in the atmospheric air of inhabited places”). Determination of volatile and limited volatile organic compounds was carried out by gas chromatographic mass spectrometry. According to the results of the identification, only trace amounts of benzyl chloride (CAS RN 100-44-7) (AESL — 0.04 mg/m3 in accordance with the SR 2.2.6.-184-2013 “Approximate exposure safe level (AESL) of pollutants in the atmospheric air of inhabited places”).

Conclusion

1. Water from sources of decentralised water supply of the Village of Kriukivshchyna and Village of Pidhirtsi is not suitable for human consumption, can be used only for technical needs, as it is contaminated with hazardous chemical compounds: petrochemicals, nitrates, ammonium nitrogen, cadmium, mercury, nickel.

2. Water of natural reservoirs near SHW landfills does not meet the established hygienic requirements: in the lake Kriuchok — by the content of ammonium nitrogen, petrochemicals and cadmium; in the lake Kupel — by petrochemicals, cadmium; in the river Siverka — by phenol, nitrates.

3. Soil near SHW landfill No. 5 is contaminated with heavy metals — lead, cadmium, and arsenic.

4. Atmospheric air near SHW landfill No. 5 has exceeded content of formaldehyde.

5. It is considered necessary to introduce environmental protection measures at the SHW landfills that will allow reducing the load on the environmental objects associated with the operation of landfills.

REFERENCES

1. Hardashuk T. V. Handling with waste as a global issue / T. V.  Hardashuk // Materials of the National Forum “Handling with waste in Ukraine: legislation, economics, technologies”, Kyiv, 2016.

2. Poviakel. L. I. Issues of hygiene and toxicology when handling with package waste / L. I. Poviakel, L. N. Smerdova // Materials of the Second Scientific and Practical Conference “Packaging industry in Ukraine”, Alushta, May 20–23, 2008. – P.142–151.

3. Ihnatenko O. P. Household waste – rules of the market game / O. P. Ihnatenko // Practical guidelines. – Kyiv, 2012. – 160 p. (fifth edition).  

4. Council Directive 1999/31/EC of 26 April 1999 on the landfill of waste.

5. Omelianenko T. L. What to expect regarding the disposal of SHW after the signing of the EU Association Agreement // T.L. Omelianenko, V. S. Mishchenko, Yu. M. Makovetska // Housing and utilities, 2014. – No. 5 (68). – P.44–47.

6. Decree of the Cabinet of Ministers of Ukraine “On the Implementation of the Association Agreement between Ukraine, for one part, and the European Union, the European Atomic Energy Community and their Member States, as part of the second part” No. 847-p as of 17.09.2014.

Надійшла до редакції 18.06.2018 р.