WIDESPREAD POPS CONTAMINATION OF SOILS IN THE BRESCIA AREA

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1 WIDESPREAD POPS CONTAMINATION OF SOILS IN THE BRESCIA AREA Marco Ciccarelli, Enrico Alberico e Massimiliano Confalonieri Agenzia Regionale per la Protezione dell Ambiente (ARPA) della Lombardia INNOVATIVE CHARACTERIZATION TECHNIQUES AND BACKGROUND VALUES 21 st September 2017, 09:15 RemTech Expo 2017 (20, 21, 22 Settembre) Ferrara Fiere Congressi, Ferrara

2 TERRITORIAL SURVEY: PROVINCE OF BRESCIA

3 THE CAFFARO INDUSTRIAL SITE Soda production factory (Kellner-Solvay method with mercury cathode and graphite anode) active since 1905 in the urban area of Brescia In 1912, the production of chlorinated products (copper oxyclurry), monoclorobenzol for the First World War and pesticides based on arsenic and lead starts In 1938, the production of PCB (under Monsanto trademark) and other chlorinated products starts. Caffaro is the only PCBs production site in Italy In 1950, the production of insecticides starts (lindano, DDT, pentaclorofenolo, ecc.)

4 CONCEPTUAL MODEL OF POPS DIFFUSION FROM CAFFARO FIELDS IRRIGATION DIFFUSION OF CONTAMINANTS FLOW AND TRANSPORTATION WITHIN IRRIGATION CHANNELS INDUSTRIAL ACTIVITY DISCHARGE IN SURFACE WATERS DREDGING OF BEDS SHUFFLING OF CONTAMINANTS

5 THE QUESTION HOW TO DISCRIMINATE POPS? POPS FROM INDUSTRIAL ACTIVITIES POPS FROM CAFFARO RELEASED IN THE ENVIRONMENT THROUGH SURFACE WATER FLOW

6 SAMPLE POINTS 30 soil samples for agricultural use according to UNI EN ISO For the control of the effects of a point source on the territory, the scheme proposed by Metodi di Analisi chimica del Suolo of the Ministry of Agriculture and Forestry has been used, which provides that punctual samples should be carried out according to a concentric sampling scheme As a "point source of alteration" was considered the Caffaro industry, with a maximum distance from the source of about 15 km and progressive rays of 5 km.

7 SAMPLE POINTS

8 TOTAL PCB CONCENTRATION IN SOILS (mg/kg) The soil samples analyzed always show PCB (µg/kg) and PCDD-PCDF (ng I-TEQ/kg) concentrations lower than CSC for public green, private green and residential areas except for one single sample number of samples average value minimum value maximum value standard deviation median 90 percentile 95 percentile 30 11,7 1,3 67,9 15,1 5,7 22,3 44,3 29 (no outlier) 9,8 1,3 47,9 10,9 5,6 18,6 32,1

9 TOTAL PCB CONCENTRATION IN SOILS (mg/kg)

10 TOTAL PCB VS CSC RATIO IN SOILS (NO OUTLIER)

11 TOTAL PCB FREQUENCY DISTRIBUTION OF RESULTS ORDERED SAMPLES WITH INCREASING CONCENTRATION

12 TOTAL PCB STATISTIC µg/kg s.s. PCB total percentile vs concentrations popolazione 1 popolazione 2 outlier Lineare (popolazione 1) Lineare (popolazione 2) percentili

13 TOTAL PCB ENVIRONMENTAL POLLUTION OF CAFFARO CAFFARO INDUSTRY

14 SIGNIFICANCE OF THE PCB CONGENERS 209 different congeners, depending on the degree of chlorination SURVEY Search for total PCBs by comparison with commercially available PCBs mixtures (Aroclor) with different chlorine content SURVEY 2006 ARPA search for 33 congeners (both dioxin-like or not) higher than those indicated by APAT, selected by taking into account the peculiarity of the Caffaro industrial production (expecially the PCB209 congener) MAY 2005 APAT defines the 28 congeners to search for, selected among those that constitute a major health risk factor and the most persistent in the environment TIME 2000 Oggi

15 CONGENERIC DISTRIBUTION OF BACKGROUND VALUES PCB CONCENTRATION PROFILE TIME

16 PCB 28 PCB 52 PCB 77 * PCB 81 * PCB 95 PCB 99 PCB 101 PCB 105* PCB 110 PCB 114* PCB 118* PCB 123* PCB 126* PCB 128 PCB 138 PCB 146 PCB 149 PCB 151 PCB 153 PCB 156* PCB 157* PCB 167* PCB 169* PCB 170 PCB 177 PCB 180 PCB 183 PCB 187 PCB 189* PCB 194 PCB PCB 209 CONGENERIC DISTRIBUTION OF CAFFARO PCB VS BACKGROUND VALUES 40% 35% 30% 25% 20% 15% 10% 5% TIME 0% Media aree agricole (375 campioni) Media punti controllo (29 punti)

17 DIOXIN AND FURANS CONCENTRATION IN SOILS (mg/kg) CSC for public green, private green and residential areas is 10 ng I-TEQ/kg (d.lgs 152/06) One sample with 13 ng I-TEQ/kg (Brescia R4) exceeds CSC number of samples average value minimum value maximum value standard deviation median 90 percentile 95 percentile 30 2,1 1,0 13,0 2,3 2,0 3,0 4,1 29 (no outlier) 1,8 1,0 5,0 1,0 2,0 3,0 3,0

18 DIOXINE AND FURANS (ng I-TEQ/kg s.s.)

19 DIOXINE AND FURANS (ng I-TEQ/kg s.s.) ORDERED SAMPLES WITH INCREASING CONCENTRATION

20 PCDD PCDF ENVIRONMENTAL POLLUTION OF CAFFARO CAFFARO INDUSTRY

21 CONGENERIC DISTRIBUTION OF CAFFARO DIOXINE VS BACKGROUND VALUES

22 NUMBER OF SAMPLES AVERAGE VALUE MAXIMU M VALUE MINIMUM VALUE STANDARD DEVIATION MEDIAN 90 %ile 95 %ile CSC GREEN NUMBER OF SAMPLES AVERAGE VALUE MAXIMU M VALUE MINIMUM VALUE STANDARD DEVIATION MEDIAN 90 %ile 95 %ile CSC GREEN POPS POLLUTION OF CAFFARO VS BACKGROUND VALUES SOIL SURVEY NATURAL BACKGROUND FARM SOILS survey FARM SOILS survey Total PCB concentration in soils (mg/kg): comparison with farm soils 60 SOIL SURVEY NATURAL BACKGROUND FARM SOILS survey FARM SOILS survey ,8 5,0 1,0 1,0 2,0 3,0 3, ,7 321,0 2,0 55,5 20,5 106,0 150, ,0 94,0 1,0 14,6 5,0 19,0 36,0 Total PCDD PCDF concentration in soils (ng I-TEQ/kg): comparison with farm soils 10

23 TOXIC EQUIVALENCY FACTOR

24 CONCLUSIONS The soil samples analyzed always show PCB (µg/kg) and PCDD-PCDF (ng I-TEQ/kg) concentrations lower than CSC for public green, private green and residential areas except for one single sample coming from Caffaro area All statistical descriptors show significant differences between the two sets of data: for the background values, the median (50 percentile) of the PCBs totals mg/kg, about 10 times lower than CSC (0.06 mg / kg), against a measured value in the southern SIN farm areas ( ) of 0.21 mg/kg (about 3.5 times the CSC) The median PCDD-PCDF concentrations for the background values are 2 ng I-TEQ/kg (5 times lower than the CSC) while in the southern SIN farm areas ( ) is 20.5 ng I- TEQ/kg (about twice the CSC). The characteristic background value (with the 95th percentile criterion) of the areas outside the SIN is 32.1 μg/kg for PCBs and 3.0 ng I-TEQ / kg for PCDD-PCDF. These values are considerably lower than those found in southern SIN farm areas. The specificity of the pollution of the south of the Caffaro Industry is highlighted

25 BIBLIOGRAPHY UNI (2011) Norma UNI EN ISO Guida alla determinazione dei valori di fondo Agenzia per la Protezione dell Ambiente e per i Servizi Tecnici e Istituto Superiore di Sanità (2006). Protocollo Operativo per la determinazione dei valori di fondo di metalli/metalloidi nei suoli dei siti d interesse nazionale Beretta G. P., Bonuomo M., Pellegrini R., Imparato V., Raffaelli L., Bracco P., Rizzi S. (2003). Linee guida per la determinazione dei valori di fondo naturale nell ambito della bonifica dei siti contaminati Provincia di Milano e Università degli Studi di Milano Ciccarelli M., Tedesco M. L., Zaniboni S., Alberico E., Confalonieri M.P. (2015) Il sito d interesse nazionale Brescia - Caffaro, risultati delle indagini svolte dall ARPA sui suoli contaminati dall industria Caffaro. Recover N.32 Tedesco M. L., Zaniboni S., Ciccarelli M., Alberico E., Oneda G. P. (2015) Indagini integrative e attualizzazione delle conoscenze per la bonifica dell area Caffaro (Brescia). Atti del workshop SiCon Siti Contaminati, Taormina 5-7 febbraio 2015 Ruzzenenti M. (2001). Un secolo di cloro e PCB, Storia delle Industrie Caffaro di Brescia, Ed. Jaka Book SpA, Milano Ministro per le Politiche Agricole. D.M. 13/09/ Approvazione dei Metodi ufficiali di analisi chimica del suolo", Gazz. Uff. Suppl. Ordin. n. 248 del 21/10/1999

26 THANKS FOR THE ATTENTION Marco Ciccarelli, Enrico Alberico e Massimiliano Confalonieri Agenzia Regionale per la Protezione dell Ambiente (ARPA) della Lombardia phone: m.ciccarelli@arpalombardia.it e.alberico@arpalombardia.it m.confalonieri@arpalombardia.it