Merja Eurola Research Scientist MTT Agrifood Research Finland Risk Assessment and Methods of Determination of Contaminats in soil TAIEX Workshop AGR Azerbaijan, Baku,

Goverment Decree on the Assement of Soil Contamination and Remediation needs Based on assessment of hazard to HEALTH or ENVIRONMENT Things to consider in the assessment of harmful substances in the soils concentration overall amounts properties location background concentration soil and groundwater conditions possibility of spreading purpose of the use for the area the severity of the health and environment hazard possible combined effects of substances Background concentration, threshold value, lower and upper guideline value have beed defined for the contaminanats – these values help the assessment

Goverment Decree on the Assement of Soil Contamination and Remediation needs Soil is regarded contaminated In industrial, storage or transport are or corresponding are if the concentration of one or several harmful substances exceed the upper guideline value In other areas soil is contaminated if the concentration of one or several harmful substances exceed the lower guideline value Guideline value have been defined by their ecological risks or health risks Reliable assessment requires Representative sampling Strandardized or corresponding reliable/validated methods Standardized methods are not always available

Examples of threshold and guideline values for contaminants in soils in Finland Substance (symbol)NaturalThresholdLower guidelineHigher guideline concentrationvalue mg/kg Arsenic (As)1 (0,1-25) Mercury (Hg)0,005 (<0,005-0,05)0,525 Cadmium (Cd)0,03 (0,01-0,15)11020 Lead5 (0,1-5) PAH PCB 0,10,55 DDT-DDD-DDE 0,112 Atrazine 0,0512 Petrol fractions (C5- C10) Petroleum fractions (>C10-C40) 300 Trichlorobenzenes 0,1520 Hexachlorobenzene 0,010,052 Dichlorophenols 0,5540

Goverment Decree on the Assement of Soil Contamination and Remediation needs Assessment must be done if the one or several harmful substances exceed the threshold value If the background concentration is higher than the threshold value, the background concentration is regarded as threshold value Risk assessment should consider soil conditions and land use, maybe toxicity and leaching tests Main receptors: groundwater, surface water, food safety, ecosystems Laboratory should be accredited or should poses a quality control system

Risk Assessment “Polluter pays” – principle In Finland polluter is first responsible for remediation, secondly the land owner if the polluter cannot be legally addressed and finally community/government (public authorities) Not always applicable principle (historical contamination, large scale transboundary contamination) Polluter does not exist anymore, cannot be identified, may not be able to pay remediation Land user cannot be held responsible for all diffuse inputs

What does accreditation mean? Accreditation is a procedure to recognize a laboratory’s competence and reliability to carry out specific tasks/tests → CERTIFICATE Public authorities, industry an commerce usually require this evidence of competence before co-operating with the laboratory In Finland FINAS (Finnish Accreditation Service) organizes accreditation activities according to the standard EN ISO/IEC General reguirements for the competence of testing and calibrationg laboratories Assessment srenghtens quality management and technical competence of the laboratory and promotes to continuous improvement Laboratories need to have programme and policy for quality assurance paricipate and show performance in proficiency testing in the scope

Determination of metals from soil Choice of the method depends on analytical need Total concentration vs. soluble concentrations Guideline values are total concentrations Aqua regia -extraction is recommended for metal analyses Does not extract metals that are strongly bound to silicate minerals Extracts about 80% of metals Internationally comparable method Information of soluble concentrations help in risk assessment (solubility of the toxic substance, bioavailability to plants, animal, micro-organisms) Different methods available for extraction of soluble fraction of metals like, AAAc-EDTA extraction Besides contaminant analyses, it is also recommended to analyse other soil parameters for example pH and electrical conductivity, organic carbon, soil type which control the fate and transport of substances in soils

Determination of metals from soil Measurement of metals AAS: grafite furnace-AAS, flame-AAS, hydride formation –AAS (As, Se), cold vapour-AAS (Hg) ICP-OES ICP-MS, lowest detection limits Mercury analyser Varian Grafite furnace AAS

Organic contaminants in soils Organic contaminants are volatile/biodegradable Bioavailability of organic contaminants can change over time due complexation, degradation, loss by volatilization, runoff or leaching Most immobile contaminants are hydrophobic and lipophilic and bind strongly to organic material and soil particles Organic carbon material affects the bioavailablility of organic compounds ParametersHolding time Solvents24 h VOX24 h Phenols24 h Chlorinated pesticides and PCB7 days TPH24 h PAH7 days MetalsUnlimited Mercury15 days

Determination of organic contaminants from soil Choice of a solvent and solvent system depend on the matrix, physical properties of analytes, equipment available No single solvent is universal: acetone/hexane or heptane, methylene chloride/acetone, toluene/methanol, heptane, pentane etc. Extraction systems: separatory funnel, Soxhlet extractor, microwave oven, supercritical fluid extraction Extract is concentrated, often exchanged into a solvent compatible with further analyses Soil sample including semi- volatile and non-volatile compounds Solvent extraction Concentration, exchange into other solvent Measuremet Clean-up procedure

Measurement of organic contaminants Measurement with chomatography GC-FID, GC-MS, HPLC, LC-MS Microwave digestion

Uncertainty of measurements No measurement is exact Quantification of the doubt about the measurement result Systematic and random error, expanded uncertainty 95% confidence limit Expressing results Same units as in legislation Cd 11 ± 2 mg/kg Uncertainty has to be taken into account when comparing results to guideline values Cd lower guideline value 10 mg/kg, result 11 ± 2 mg/kg 11-2 = 9 mg/kg result is under the guideline value Cd result 13 ± 2 mg/kg 13-2 =11 mg/kg result exceeds the guideline value

Soil quality stardard methods ISO 11466:2007 Soil quality. Extraction of trace elemets soluble in aqua regia. ISO 11047:2007 Soil quality. Determination of cadmium, chromium, cobalt, copper, lead, manganese, nickel and zinc in aqua regia extracts of soil. Flame and electrothermal atomic absorption spectrometric methods, ISO 14154:2007 Soil quality. ISO 10382:2007 Soil quality. Determination of organochrine pesticides and poluchlorinated biphenyls. Gas choromatographic method with electron capture detection ISO 15009:2007 Soil quality. Gas chormatographic determanation of the content of volatile aromatic hydrocarbons, naphtalenen and volatile halogenated hydrocarbons. Purge-and-trap method with thermal desorption. ISO 16287:2007 Soil quality. Determination of polycyclic aromatic hydrocarbons (PAH). Gas chromatographic method with mass spectrometric detection (GC-MS) ISO 22155:2007 Soil quality. Gas chromatographic quantitative determination of volatile aromatic and halogenated hydrocarbons and selected ethers. Static headspace method. ISO 16703:2007 Soil quality. Determination of content of hydrocarbon in the range of C10 to C40 by gas chromatography. ISO 11264;2007 Soil quality.Determination of herbicides. Method using HPLC with UV-detection.

Risks in Agriculture Contamination in agriculture Sources: atmospheric deposition, fertilizers, applications of pesticides, manure, sludges, biowastes Risks: accumulation of persistent contaminants, leaching rates of contaminants to water ecosystems, food safety The farmer should be encouraged to for good agricultural practises and sustainable use of land → farmer needs support like guidelines for applications, training, help in economic issues etc. Long term goal: balanced inputs and outputs (nutrients, metals, pesticides), so that healthy soil is maintained, concentrations of food products meet the standards and leaching to groundwater is minimized

Cadmium in Finnish agro-ecosystems Ritva-Mäkelä-Kurtto et. al Risk assessment of Cd in fertilizers using international models 3 crops were studied: wheat, potato, sugar beet Cd concentration 2.5 mg/kg P (present content in Finland) → inputs and output in balance Cd concentration 50 mg/kg P (maximum allowed content) → in 100 years Cd in soil and soil water would increase 10-50%, in crops 5-15% Cd concentration 138 mg/kg P (average content in P fertilizers in Europe) → in 100 years Cd in soil and soil water would increase %, in crops 20-40% Greatest increase was in potato cultivation

Degree of Ministry of Agriculture and Forestry 12/2007 Limit values for harmful metals in fertilizers Limit value for Cd in mineral fertilizer containing at least 2.2% P is 30 mg/kg P Highest Cd load from fertilizers must not exceed 1,5 g/ha for one year or 6 g/ha for four years ElementLimit value mg/kg dm Arsenic, As25 Mercury, Hg1,0 Cadmium, Cd1,5 Cobalt, Co300 Chrome, Cr300 Copper, Cu600 Lead, Pb100 Nickel, Ni100 Zinc, Zn1500

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