Analysis of monitoring programs and their suitability for ecotoxicological risk assessment in four Spanish basins
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1 Analysis of monitoring programs and their suitability for ecotoxicological risk assessment in four Spanish basins J.C. López Doval 1, N. De Castro Català 1, I. Andrés Doménech 2, J. Blasco 3, A. Ginebreda 4, I. Muñoz 1 1 Department of Ecology, UB 2 Department of Hydraulic Engineering and Environment, UPV 3 Department of Ecology and Coastal Management, Institute of Marine Sciences of Andalucia, CSIC 4 IDAEA CSIC
2 OBJECTIVES The main objective is to evaluate whether a potential risk (measured as TU) accurately reflects the risk to the community or, alternatively, whether new criteria should be developed to improve the risk assessment.
3 OBJECTIVES Two approaches: 1. To identify those chemicals most likely responsible for the environmental toxicological risk in four Spanish Mediterranean basins (as case studies) 2. To investigate the relationships between toxicological risk and biological status in these catchments.
4 STUDY SITE Ebro Llobregat Júcar Guadalquvir
5 MATERIAL AND METHODS: basin data base Data from Confederación Hidrográfica del Ebro (CHE), Confederación Hidrográfica del Jucar (CHJ), Confederación Hidrográfica del Guadalquivir/Agencia Andaluza del Agua (CHG/AAA), Agència Catalana de l Aigua (ACA) databases. Data obtained from sampling points included in the quality monitoring programs. Sites studied here were those where priority substances and other hazardous substances were periodically measured. From ( for Guadalquivir data). To study the relationship between toxicological risk and biological quality we selected those sites where macroinvertebrates and chemicals were sampled together.
6 MATERIAL AND METHODS: potential toxic risk The analysis of toxic units (TU) results in each monitoring site is intended to localise and evaluate the potential toxicological risks for the communities.
7 MATERIAL AND METHODS: potential toxic risk Use of data provided by water agencies on concentration of organic pollutants and metals. Use of the toxic unit (TU) concept to evaluate the toxicological risk at each sampling point. The TU quantifies the toxic stress associated with a mixture of pollutants and is defined as the ratio of a chemical's concentration and its observed LC 50 for Daphnia magna.
8 MATERIAL AND METHODS: potential toxic risk ToxicUnits = TU = n n = i TU i i= 1 i= 1 50 C LC i
9 MATERIAL AND METHODS: potential toxic risk The resulting value can be used to assess the risk to the macroinvertebrate community. For each year and sampling point we used the maximum annual concentration measured ( worst case scenario). Compounds that have never been detected above the limit of quantification (LOQ) were excluded.
10 MATERIAL AND METHODS: relationships between chemical and biological status The response of the macroinvertebrate community to potential toxicological risk in the studied river basins was evaluated through analysis of biological data compiled by the water authorities and compared with TU results obtained.
11 MATERIAL AND METHODS: relationships between chemical and biological status Only sites where both chemical and biological data were available were studied. log TU vs IBMWP or SPEAR indexes. IBMWP index was provided by the water agencies. This index is based in the presence or absence of different invertebrate families SPEAR index was calculated by us. This index is based in biological traits, and the absence of sensitive families (more information in systemecology.eu/spear/start.html). Calculation Spearman's correlation coefficient (significant correlation for p>0.05).
12 RESULTS: river basin database Year 2010 Llobregat Júcar Ebro Guadalquivir Total number of monitoring sites Total data entries per year Total number of chemical monitoring sites Total number of biological monitoring sites Total number of sites where PS and other hazardous substances were periodically measured Number of chemical compounds analyzed Number of chemical compounds >LOQ Number of PS analyzed Number of PS above maximum EQS Summary of data provided by water agencies
13 RESULTS: river basin database Year 2010 Llobregat Júcar Ebro Guadalquivir Total number of monitoring sites Total data entries per year Total number of chemical monitoring sites Total number of biological monitoring sites Total number of sites where PS and other hazardous substances were periodically measured 28 in the Ebro Number 50 in Guadalquivir of chemical compounds analyzed Number of chemical compounds >LOQ in Júcar 25 in Llobregat Number of PS analyzed Number of PS above maximum EQS
14 RESULTS: river basin database Year 2010 Llobregat Júcar Ebro Guadalquivir Total number of monitoring sites Total data entries per year Total number of chemical monitoring sites Total number of biological monitoring sites Total number of sites where PS and other hazardous substances were periodically measured Number of chemical compounds analyzed Number of chemical compounds >LOQ Number of PS analyzed Number of PS above maximum EQS
15 RESULTS: river basin database Year 2010 Llobregat Júcar Ebro Guadalquivir Total number of monitoring sites Total data entries per year Total number of chemical monitoring sites Total number of biological monitoring sites Total number of sites where PS and other hazardous substances were periodically measured Number of chemical compounds analyzed Number of chemical compounds >LOQ Number of PS analyzed Number of PS above maximum EQS
16 RESULTS: river basin database The parameters analysed varied by sampling point and by basin. For the chemical parameters, spatial coverage and sampling frequency varied by parameter, year and basin.
17 RESULTS: river basin database Year Number of stations Max. num. of compounds analyzed Min. num. of compounds analyzed Stations where only metals are analyzed Stations where only organic are analyzed Stations where both are analyzed Ebro Guadalquivir Júcar Llobregat
18 RESULTS: river basin database Year Number of stations Max. num. of compounds analyzed Min. num. of compounds analyzed Stations where only metals are analyzed Stations where only organic are analyzed Stations where both are analyzed Ebro Guadalquivir Júcar Llobregat
19 RESULTS: river basin database Year Number of stations Max. num. of compounds analyzed Min. num. of compounds analyzed Stations where only metals are analyzed Stations where only organic are analyzed Stations where both are analyzed Ebro Guadalquivir Júcar Llobregat
20 RESULTS: river basin database Year Number of stations Max. num. of compounds analyzed Min. num. of compounds analyzed Stations where only metals are analyzed Stations where only organic are analyzed Stations where both are analyzed Ebro Guadalquivir Júcar Llobregat
21 RESULTS: potential toxic risk Only 13 to 24 compounds were used for TU calculation. The higher toxicity risk is associated with the presence of metals in most of the sites. This risk is associated with the presence of Zn and Cu. Toxicity risk associated to organic compounds is scarce and pesticides or their derivates are the responsible when it occurs. Sites with absence of chemical risk are rare.
22 RESULTS: potential toxic risk TU as total sum of all TU values for each compound in the mixture of pollutants (TU Zn +TU Cu +TU Cr )
23 RESULTS: potential toxic risk Compounds represented are those that contribute more than 95% of the total toxicological risk
24 RESULTS: potential toxic risk The weight of metals in total toxicity is very important
25 JÚCAR RESULTS: potential toxic risk
26 JÚCAR RESULTS: potential toxic risk
27 RESULTS: potential toxic risk GUADALQUIVIR
28 RESULTS: potential toxic risk LLOBREGAT & EBRO
29 RESULTS: relationships between chemical and biological status Significant relationship between biological indexes (IBMWP and SPEAR) and toxic risk (TU) only in Llobregat river.
30 RESULTS: relationships between chemical and biological status toxic risk SPEAR index, designed for assessment of impacts of pesticides on macroinvertebrates Log TU org, toxic risk for pesticides Log TU org D. magna Thresholds for log TU: uncontaminated (log TU < 4) slightly contaminated Log TU tot D. ( 4 magna > log TU < 2) highly contaminated (log TU > 2)
31 RESULTS: relationships between chemical and biological status toxic risk toxic risk Log TU org D. magna Log TU tot D. magna Log TU tot = Log TU org + Log TU metal
32 RESULTS: relationships between chemical and biological status No clear relationships between biological indexes (SPEAR and IBMWP)and toxic risk (TU) in Ebro, Guadalquivir or Jucar
33 RESULTS: relationships between chemical and biological status toxic risk toxic risk Log TU org D. magna Log TU tot D. magna
34 DISCUSSION & CONCLUSIONS High toxic risk for biota in base to TU results in most of the studied points (especially for metals) was expected
35 DISCUSSION & CONCLUSIONS High toxic risk for biota in base to TU results in most of the studied points (especially for metals) was expected No clear relationships between biological quality and potential risk
36 DISCUSSION & CONCLUSIONS High toxic risk for biota in base to TU results in most of the studied points (especially for metals) was expected Why? No clear relationships between biological quality and potential risk
37 DISCUSSION & CONCLUSIONS ARE METALS LESS TOXICANT AS WE THOUGH? Are there a background level of metals? Have the organisms developed tolerance? Are LC 50 values found in bioassays for invertebrates overestimating the toxicity? Should be better analyze bioavailable fractions instead of total content of metals? Have we include new methods in monitoring programs in order to assess the real impacts in fauna? (in situ bioassays, use of biomarkers)
38 DISCUSSION & CONCLUSIONS Any suggestion for the improvement of data bases?
39 DISCUSSION & CONCLUSIONS The sampling routines of the water agencies were sufficient to monitor the water quality under WFD specifications. The data sets were not homogeneous across basins. It is also important to increase the number of sampling sites where chemical and biological data could be taken together. Extensive chemical monitoring in these points is desirable. Due to the high number of compunds with values below LOQ, the analytical procedures for some of these substances need improvement. With respect to field data sets, the collection of long term data is also recommended. The introduction of new chemical compounds, susceptible of having effects on biota, should be included in monitoring programs.
40 THANKS FOR YOUR ATENTION
41 The authors would like to acknowledge the Confederación Hidrográfica del Ebro (C. Durán and V. Sánchez Tello), Confederación Hidrográfica del Guadalquivir (V. Cifuentes), Agencia Andaluza del Agua, Agència Catalana de l'aigua (A. Munné, L. Tirapu) and Confederación Hidrográfica del Júcar (MA Piñón) which kindly provided the monitoring data. Núria De Castro Català holds a predoctoral grant from the University of Barcelona.
Document downloaded from: This paper must be cited as:
Document downloaded from: http://hdl.handle.net/0/ This paper must be cited as: Andrés Doménech, I.; Isabel Muñoz; Antoni Ginebreda; Julian Blasco; Núria De Castro- Català; Julio C. López-Doval (0). Analysis
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