Ecotoxicity of river sediments:

invertebrate community, toxicity

bioassays and the Toxic Unit approach as

complementary assessment tools Núria de Castro-Català, Maja Kuzmanovic, Neus Roig, Jordi Sierra, Antoni Ginebreda, Damià

Barceló, Sandra Pérez, Mira Petrovic, Yolanda Picó, Marta Schumacher and Isabel Muñoz

INTRODUCTION

Sediment quality is crucial to the health of an aquatic

ecosystem.

Efficient extraction technologies and liquid chromatography

mass spectrometry (LC-MS)

Picó et al. 2015 Anal Bioanal Chem

INTRODUCTION

Chemical concentrations alone are insufficient to

demonstrate adverse environmental effects because they

do not provide evidence of toxicity

Bioavailability depends upon hydrological conditions,

sediment composition, organic matter content, ...

Different modes of action, different sensitivities of the

organisms

OBJECTIVES Multi-stressed river basins from the Iberian Peninsula

4 – 5 sampling sites in each River

OBJECTIVES

Pollutants

Toxicity

What kind of toxicity?

How much?

Pollutants

Organic compounds:

POPs, Pests, PhACs, EDCs, PFCs

OBJECTIVES

POPs (Persistent Organic Pollutants)

PAHs (Polycyclic aromatic hydrocarbons):

- fossil fuels and in tar deposits

- result of incomplete combustion of organic matter

PCBs (Polychlorinated biphenyls):

- used as dielectric and coolant fluids

- banned by the United States Congress in 1979 and by the

Stockholm Convention on Persistent Organic Pollutants in 2001.

EDCs (Endocrine Disrupting Compounds)

Azoles corrosion inhibitors

Bisphenol A

Parabens

preservatives in cosmetics and pharmaceuticals

Estrogens

Alkylphenols detergents, fuels and lubricants,

phenolic resins, fragrances, antioxidants, oil field

chemicals and fire retardant materials

Others…

PFCs (Perfluorinated compounds)

used in textiles and food packaging due to their unique

properties as repellents of water and oils

also used as surfactants and lubricants in fire-fighting foams,

pesticides and personal care products

©4-seasons.de ©chemicalfreelife.tumblr.com © kangahoo.com

Pollutants

Organic compounds:

POPs, Pests, PhACs, EDCs, PFCs

Metals

Pore water and whole sediment

BCR sequential extraction, AVS and SEM

Sediment characterization

Grain size, organic carbon and organic matter content

OBJECTIVES

Toxicity risk assessment:

Toxic Units

Toxicity tests

Whole sediment tests

Pore water tests

Invertebrate community

OBJECTIVES

Toxic units Sprague and Ramsay, 1965

MATERIALS AND METHODS

Toxic units

Di Toro et al., 1991

Höss et al., 2011

CS = CPW × Kd

MATERIALS AND METHODS

Organic compounds (WS)

Metals (PW)

Concentration Addition model => ΣTUs

Vibrio fischeri

15min acute test

(Microtox)

Daphnia magna

48h acute test

Pseudokirchneriella

subcapitata

72h growth test

Chironomus riparius

10d chronic test O

rgan

ism

co

mp

lexi

ty

Duration of the test

Relevance at the community level

MATERIALS AND METHODS Toxicity tests

© J.W. Hastings

© www.algalweb.net/

© N. Hopkins

© mblaquaculture.com

Vibrio fischeri

15min acute test

(Microtox)

Daphnia magna

48h acute test

Pseudokirchneriella

subcapitata

72h growth test

Org

anis

m c

om

ple

xity

Duration of the test

MATERIALS AND METHODS

PORE WATER Chironomus riparius

10d chronic test

Vibrio fischeri

15min acute test

(Microtox)

Daphnia magna

48h acute test

Pseudokirchneriella

subcapitata

72h growth test

Chironomus riparius

10d chronic test

Org

anis

m c

om

ple

xity

Duration of the test

MATERIALS AND METHODS

WHOLE SEDIMENT

-Community composition

- Abundances

Canonical Correpondence Analyses

Macroinvertebrate communities of the sediment

MATERIALS AND METHODS

RESULTS. Metals µg/g DW

A residual

B organic matter / sulphides

C Fe Mn oxyhydroxides

D exchangeable / carbonates

US EPA benchmark

RESULTS. Metals

Pore water metals above the US EPA benchmarks:

Hg 0-0.25 µg/L As 4-140 µg/L

Cu 1-60 µg/L

SEM/AVS ratio > 1 in J4, G2, G4 and E2

RESULTS. Organic compounds

PAHs (e.g., chrysene, pyrene, phenanthrene)

EDCs (e.g., nonylphenol, methylparaben)

RESULTS. Organic compounds TUs

RESULTS. Organic compounds TUs

Organophosphate

insecticides

RESULTS. Metals TUs

RESULTS. Macroinvertebrate communities

CCA

12% of the total inertia

F. Chironomidae

P. Oligochaeta

Richness decreased

downstream

Polypedilum sp.

Branchiura sowerbyi

Limnodrilus hoffmeistieri

Short-term (15 min to 72 h)

Whole sediment Pore water

V.fischeri V.fischeri P.subcapitata D.magna

Sample EC50 EC50 EC50 EC50

(mg/l) (%vol:vol) (%vol:vol) (%vol:vol)

E1 5348 43.4 183 >100

E2 1488 47.4 229 >100

E3 1421 72.8 101 >100

E5 5087 55 121 >100

G1 814 >100 131 >100

G2 664 >100 129 >100

G3 31.1 >100 76 >100

G4 87.7 51.5 89 >100

J2 2157 70.6 66 >100

J4 5127 >100 101 >100

J5 586 >100 147 >100

J6 902 >100 172 >100

J7 3092 >100 116 >100

L3 3244 >100 227 >100

L4 11682 >100 321 >100

L5 3076 >100 28 >100

L7 1729 >100 50 >100

RESULTS. Toxicity tests

RESULTS. Toxicity tests Long-term (10 days)

Whole sediment C. riparius

Sample mortality development biomass

% HW (mm) %control DW (mg) %control

E1 50 0.56 103 0.46 98

E2 20 0.54 100 0.42 90

E3 0 0.53 97 0.24 51

E5 0 0.57 104 0.53 112

G1 10 0.55 101 0.34 73

G2 0 0.54 100 0.17* 36*

G3 0 0.55 102 0.30 63

G4 0 0.50 92 0.29 61

J2 20 0.58 107 0.90** 192**

J4 0 0.56 104 0.43 91

J5 30 0.57 105 0.50 107

J6 0 0.56 104 0.45 96

J7 10 0.56 104 0.49 104

L3 10 0.56 103 0.47 100

L4 20 0.55 102 0.28 59

L5 30 0.45 83* 0.23 49

L7 0 0.51 95 0.30 64

Dunnett’s post-hoc tests,

*p<0.05, **p<0.01

C. riparius

Mortality – TUs Chlorpyrifos

Development and biomass – TUs PhACs

V. fischeri

Whole sediment – TUs PhACs

Pore water – TUs metals (Ni)

Hg

RESULTS. Significant Spearman rank correlations

p<0.05

Highest toxicity:

L5, E1 and J5

Guadalquivir river

Júcar river

DISCUSSION

- High toxicity of OPs insecticides

Chlorpyrifos effects at µg/L level, bioaccumulation

(Pérez et al., 2013, Masiá et al., 2015)

DISCUSSION

- High toxicity of OPs insecticides

Chlorpyrifos effects at µg/L level, bioaccumulation

(Pérez et al., 2013, Masiá et al., 2015)

Malathion, diazinon and chlorfenvinphos

(Rebechi et al., 2014; Schuler et al., 2005)

DISCUSSION

- Toxicity of metals for unicellular organims

Cu, Ni, Hg, Zn

(Lemire et al., 2013)

- Effects at the community level

POPs (PAHs), Pests

Importance of sediment dynamism

(Buendia et al., 2013)

DISCUSSION

CONCLUSIONS

The combination of the TUs approach, the battery of toxicity

tests and the description of the invertebrate communities

helped us to identify OPs insecticides and some metals as the

main contributors to the sediment toxicity.

Moltes gràcies!

Acknowledgements

This study was funded by the Spanish Ministry of Economics and Competitiveness through the project

SCARCE (Consolider-Ingenio 2010 CDS2009-00065). We are especially grateful to Laura Armendáriz

for the identification of the Oligochaeta, and to those who assisted us in the field and helped us to obtain

data, especially, Júlio C. López-Doval and Patricia Rodrigo.

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