Licia Guzzella CNR-IRSA Brugherio (MB) Microinquinanti & contaminanti emergenti, 11 e 12 Giugno 2018, Milano 1

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1 Licia Guzzella CNR-IRSA Brugherio (MB) Microinquinanti & contaminanti emergenti, 11 e 12 Giugno 218, Milano 1

2 Which items? a. Monitoring Strategy: WFD Directive 2/6 requires evaluation of aquatic ecosystems according to operative, surveillance or investigation monitoring. According to monitoring type, environmental compartment of concern, temporal and spatial variability and trends, different trophic levels, physiological status and exposure pathway of organisms must be considered b. Behavior : interaction between abiotic and biotic compartments: - Bioavailability - Toxic effects measured at different levels of biological organization (from molecular to community level) c. Last but not least - Risk : biodegradation and metabolic activation, different use of waters, relation between aquatic and terrestrial ecosystems Microinquinanti & contaminanti emergenti, 11 e 12 Giugno 218, Milano 2

3 a n aziende a scala comuna Monitoring Strategy "peso 1" Directive 2/6 and Italian Law 215/ no idrografico T. Seveso colo idrografico Which contaminants? "peso 2" ni idrici -3 Legenda ti comunali Selection follows actual priority and hazardous substance list, but also must be integrated with analysis of Seveso River anthropogenic pressures. basin with 4-8 idrografico T. Seveso Bacino de a scala comunale Bacini idrici 24 - comunali 9 Limiti 3" a scala comuna n "peso aziende -2 "peso 1" potential PBDE emissions sources idrografico Reticolo "peso 2" Aziende con peso 1 Aziende con peso 2 Aziende con peso Rain event on May 216 at 24-9 different stations of Seveso River and"peso 3" -2 concentrations of pollutants in total 3-8 suspended solids (Cr, Cd, Ni, Pb, Cu, PBDE) Da: Monitoraggio qualitativo delle acque del Torrente Seveso Rapporto IRSA, 216 3

4 Abiotic compartments: water, sediments and suspended solids River sediment grab sampling 24 hour sampling for waters According to the physicalchemical characteristics of pollutants, the matrix to be considered must be different. Sediments may be a sink or a source of contamination: for example PCB, PBDE, DDT, ect... are accumulated in sediments and suspended particulate; PCP (Personal Care Products as limonene) or PFC (PerFluorinated Compounds) are present mainly in water because of their solubility. Microinquinanti & contaminanti emergenti, 11 e 12 Giugno 218, Milano 4

5 depositional year DDx trends in a core sediment collected in the Pallanza Basin, Lake Maggiore 2/11-5/9 5/9-7/7 7/7-9/ Conc. (ng g -1 p.s.) Sediment core at station 13 Microinquinanti & contaminanti emergenti, 11 e 12 Giugno 218, Milano 5

6 ng g -1 p.s. Temporal trends: sediment cores in ng g -1 TOC ng g -1 p.s. ng g -1 TOC Lake Maggiore Brominated flame retandant used for plastic housing, syntetic textile and electronic devices. The use of tri to epta BDE (ng/g) was BANNED ,2 LM 13 - PBDE BDE-28 BDE-47 BDE-1 BDE-99 BDE-154 BDE-183 BDE-153 BDE-29 Conc. normalizzata TOC LM 28 - PBDE BDE-28 BDE-47 BDE-1 BDE-99 BDE-154 BDE-183 BDE-153 BDE-29 Conc. normalizzata TOC Deca-BDE (BDE-29) showed maximum concentrations in 211, the use of this compound is restricted. PBDE are endocrine disruptors (interfence with tyroxin ormones) and neuro-toxic. Microinquinanti & contaminanti emergenti, 11 e 12 Giugno 218, Milano 6

7 ng g -1 p.s ng g -1 p.s. Sediment trends in rivers 6 PCB Bardello River PBDE Bardello River Microinquinanti & contaminanti emergenti, 11 e 12 Giugno 218, Milano 7

8 Biotic compartment: site-specific data Benthic invertebrates: collected with hand nets in the Toce River. Specimens were separated according to taxonomic group and/or functional feeding group Coregonus lavaretus Alosa fallax lacustris Fish: collected in the Pallanza Bay using gill nets: Rutilus rutilus (roach): littoral, bentophagic Coregonus lavaretus (common whitefish) : pelagic, planktophagic Alosa fallax lacustris (landlocked shad): pelagic, planktophagic

9 ng g -1 p.s. 1 Behavior: sediment contamination in Toce (DDT and metabolites) o,p -DDE Industrial site DDE + DDD <,5 σ DDT op +pp - DDT overcome PEC value: 63 ng g -1 p,p -DDE o,p'-ddd p,p -DDD o,p -DDT p,p -DDT 2 1 aprile ottobre aprile ottobre aprile ottobre aprile ottobre aprile ottobre DOMO PRATA BOSCO TENSO PREMOSELLO ORNAVASSO Premosello (April): concentrations mean distribution of DDx: 8% of p,p -DDT DDx concentrations in sediments potentially toxic for benthic invertebrates Microinquinanti & contaminanti emergenti, 11 e 12 Giugno 218, Milano 9

10 ng g -1 p.s. Behavior: bioaccumulation in benthic invertebrates of the Toce (DDT and metabolites) G=Gammaridae D=Diptera H=Heptageniidae B=Baetidae *** Industrial site SQA Limit o,p'-dde p,p'-dde o,p'-ddd p,p'-ddd o,p'-ddt p,p'-ddt G D H B G D H B G D H B G D H B G D H B G D H B G D H B G D H B G D H B G D H B aprile ottobre aprile ottobre aprile ottobre aprile ottobre aprile ottobre DOMO PRATA BOSCO TENSO PREMOSELLO ORNAVASSO mean distribution of DDx: 6% of p,p - DDE Significant difference between upstream and downstream the industrial site According to Environmental Quality Standard for biota, Toce River is not in a good state Microinquinanti & contaminanti emergenti, 11 e 12 Giugno 218, Milano 1

11 ng g -1 p.f. ng g -1 lip. ng g -1 p.f. ng g -1 lip. ng g -1 p.f. ng g -1 lip. Fish: seasonal variability-physiological status DDT young shad 1 FL DDT - adult shad p,p -DDT o,p -DDT 6 15 p,p -DDD o,p'-ddd p,p -DDE 1 Primavera Estate Autunno Inverno DDT - whitefish o,p -DDE 8 2 Primavera Estate Autunno Inverno DDx tot norm. sul contenuto lipidico Bioaccumulation : trophic level, pre- o post-reproductive status, lipid content 2 Primavera Estate Autunno Inverno Microinquinanti & contaminanti emergenti, 11 e 12 Giugno 218, Milano 11 5

12 ng/g lw Fish: temporal trends and trophic relation Significant decrease of DDx values from 21 to 215 in both shad and whitefish p <,1 p <,1 DDx p <,1 whitefish shad p <, DDx peaks show a 3-6 months delay in comparison to peaks in zooplankton because a time span is necessary for trophic transfer 12

13 Behaviuor: Bioavailability Bioavailability may identify environmental risk: passive samplers (as PED) can be used to estimate mean average concentrations in water and to predict site-specific contamination in biota. EU Directive recommends the use of passive samplers instead of spot water samples. Microinquinanti & contaminanti emergenti, 11 e 12 Giugno 218, Milano 13

14 ng L -1 April 214 October 214 Average April 214 October 214 Average April 214 October 214 Average April 214 October 214 Average ng g -1 d.w.,5,4,3,2,1 Bioavailability: use of PED samplers in Toce River April 214 Prata Bosco tenso Premosello Ornavasso Water Pore water Heptageniidae resulted as the best site-specific bioaccumator of DDx, showing a good with porewater PED results Polyethylene (PED) samplers estimate bioavailable water levels and sediment pore waters concentrations for DDx Macrobenthos: Heptagenidae Prata Microinquinanti & contaminanti emergenti, 11 Bosco tenso Premosello Ornavasso e 12 Giugno 218, Milano 14

15 RISK : Ecological risk assessment (ERA) Site of National Interest (SIN) of Pieve Vergonte (Piedoment Region): contamination of sediments and fish species of the Toce River and the Pallanza Bay (Lake Maggiore) for DDT and mercury. Which approach for the Ecological Risk Assessment (ERA)? How to identify risk thresholds for each environmental compartment? Definition of: conceptual model of the site; receptors and exposure pathways. Industrial site at Pieve Vergonte Microinquinanti & contaminanti emergenti, 11 e 12 Giugno 218, Milano 15

16 Site specific conceptual model

17 Environmental Risk Assessment (ERA) for a contaminated aquatic ecosystem Analysis of sediments and water in the aquatic ecosystem Conceptual Site Model Analysis of bioavailability for biota Evaluation of pollutant contamination in sediment and waters Definition of screening benchmarks Evaluation of contaminant in benthic organisms Direct effects on biota Definition of risk benchmarks Direct effects on biota and secondary poisoning 17

18 DDx Comparison between on-site data and benchmarks: DDx

19 Conclusion and management directions: DDx Sediment Quality Triad for DDx Benthos Fish or other aquatic organisms Secondary poisoning Sediments Benthos Tissues Toxicity tests Ecological status Waters Fish tissues Fishing birds or bats Lake Maggiore Exceedance of attention benchmarch Exceedance of attention benchmarch No toxic effetcs Sufficient Ecological status No Exceedance of risk benchmark No Exceedance Toce River One Exceedance of risk benchmark in 29 and of attention benchmark No Exceedance Some toxic effects on C. riparius and on algae test upstream and downstream the industrial site Sufficient Ecological status No Exceedance of risk benchmark No Exceedance No Exceedance of risk benchmark Exceedance of risk benchmark or toxicity Exceedance of attention benchmark or toxicity not correlated with DDx and Hg levels No Exceedance Microinquinanti & contaminanti emergenti, 11 e 12 Giugno 218, Milano

20 Conclusions Monitoring Strategy For each specific water body, pressure analysis drives selection of contaminants, followed by matrices of concern (water, sediment, biota) studying temporal and spatial variability evaluation of trends, for biota: trophic levels, exposure mode, Behavior - Bioavailability (main strategy) - toxic effects measured at different level of biological organization Risk for human health and ecosystem impact What else? Working for improving knowledge and developing new technology!!! Microinquinanti & contaminanti emergenti, 11 e 12 Giugno 218, Milano THANK YOU! 2