perfluorinated compounds in water, sediment, and wild bird ......perfluorinated compounds in water,...

Perfluorinated compounds in water, sediment, and wild bird eggs from the Orange-Senqu River Basin, South Africa

Caitlin SwiegelaarChromSAAMS12 September 2016

TQM-5126-1

Introduction

Widespread presence in humans and

wildlife

Toxicological implications

Extensively used for over

50 years

TQM-5126-1

Introduction

TQM-5126-1

Perfluorobutanesulfonic acid

(PFBS)

Perfluorononanoic acid

(PFNA)

Perfluorohexanesulfonic acid

(PFHxS)

Perfluorodecanoic acid

(PFDA)

Perfluorooctanesulfonic acid

(PFOS)

Perfluorohexanoic acid

(PFHxA)

Perfluoroheptanoic acid

(PFHpA)

Perfluorooctanoic acid

(PFOA)

Perfluoroundecanoic acid

(PFUnA)

Perfluorotridecanoic acid

(PFTrDA)

Perfluorododecanoic acid

(PFDoA)

Perfluorotetradecanoic acid

(PFTA)

Introduction

TQM-5126-1

Levels in South Africa

Introduction

TQM-5126-1

2010 JohannesburgMaternal serum PFOS: 1.6 ng/mLPFOA: 1.3 ng/mLPFHxS: 0.5 ng/mLCord bloodPFOA: 1.3 ng/mLPFOS: 0.7 ng/mLPFHxS: 0.3 ng/mL

Hanssen, L et al., 2010. Journal of Environmental Monitoring 12: 1355-1361

Introduction

TQM-5126-1

2014 Kruger National ParkNile crocodile eggsPFOS: 14 ng/gPFDA : 1 ng/gOther PFCs: Limit of quantification (LOQ)

Bouwman,H et al., 2014. Ecotoxicology and Environmental Safety 104: 393-402

Introduction

TQM-5126-1

2015 Western CapeAfrican Penguin eggsPFOS: 10 ng/gPFOA: 6 ng/gPFNA: 9 ng/gPFDA: 2 ng/gPFUnA: 6 ng/g

Bouwman, H et al., 2015. Chemosphere 126: 1 - 10

Introduction

TQM-5126-1

2016 Kruger National ParkNile crocodile plasmaPFOS: 50 ng/gPFNA: 0.5 ng/gPFDA: 3 ng/gPFUnA: 2 ng/gPFDoA: 0.5 ng/gPFHxS: 1 ng/g

Christie, I et al., 2016. Chemosphere 154: 72 - 78

Introduction

TQM-5126-1

2013 Orange-SenquRiver BasinSediment: No detectsSharptooth catfishPFOS: 12 ng/gWild bird eggs:11 SpeciesPFOS range:5 – 2300 ng/g

Orange River BasinNossob

Fish

Molopo

Orange

VaalVaal Dam

Vanderkloof DamGariep Dam

Bloemhof Dam

Katse Dam

Bouwman, H & Pieters, R., 2013. Orasecom

Introduction

TQM-5126-1

Current study Orange-SenquRiver BasinMatrices included:WaterSedimentMine TailingsFishBird eggs

Orange River BasinNossob

Fish

Molopo

Orange

VaalVaal Dam

Vanderkloof DamGariep Dam

Bloemhof Dam

Katse Dam

Introduction

TQM-5126-1

Common name Scientific name Diet

African Darter Anhinga rufa Piscivore

Black-headed Heron Ardea melanocephala Generalist

Grey Heron Ardea cinerea Piscivore

Reed Cormorant Phalacrocorax africanus Piscivore

White Breasted Cormorant Phalacrocorax carbo Piscivore

Cattle Egret Bubulcus ibis Insectivore

Glossy Ibis Plegadis falcinellus Insectivore

Sacred Ibis Threskiornis aethiopicus Scavenger

Materials and Methods

Matrix Water SedimentBird eggs and fish

Extraction

WAX SPE

Ultrasonic (Sodium

hydroxide)

Liquid-liquid

(Methanol)

Clean-up WAX SPEENVI-Carb™



Extraction

WAX SPE

Ultrasonic (sodium

hydroxide)

Liquid-liquid

(Methanol)




Extraction

WAX SPE

Ultrasonic (Sodium

hydroxide)

Liquid-liquid

(Methanol)




Extraction

WAX SPE

Ultrasonic (sodium

hydroxide)

Liquid-liquid

(Methanol)




Extraction

WAX SPE

Ultrasonic (Sodium

hydroxide)

Liquid-liquid

(Methanol)


Evaporated and reconstituted in starting conditions of LC-MS/MS


• Analytical column:

• FluoroSep RP-Octyl column (5 µm x 150 x 2 mm)

• Mobile phase

• 5 mM aqueous ammonium formate at pH 6.2 (A) and 100% methanol (B)

• Table 1: Gradient conditions used for the separation

TimeFlow

(mL/min)% Solvent A % Solvent B

Initial

0.400

60 40

1.00 60 40

25.00 10 90

30.00 10 90

35.00 0 100

35.10 60 40

45.00 60 40

Results and discussion

PFBS

PFUnA

Water

PFOS

PFHxA PFOA

Sediment

PFHxA

Tailings


PFBS

PFUnA

Water

PFOS

PFHxA PFOA

Sediment

PFHxA

Tailings

Diamond mining and maize farming

Home and textile industries


PFBS

PFUnA

Water

PFOS

PFHxA PFOA

Sediment

PFHxA

Tailings


PFBS

PFUnA

Water

PFOS

PFHxA PFOA

Sediment

PFHxA

Tailings

Industrialized area and close to largest airport in South

Africa

Inactive gold mines


PFBS

PFUnA

Water

PFOS

PFHxA PFOA

Sediment

PFHxA

Tailings


PFBS

PFUnA

Water

PFOS

PFHxA PFOA

Sediment

PFHxA

Tailings

Inactive gold mines


No PFCs detected in the fish


Levels in bird species


Figure 1: The ΣPFCs distribution according to chain length

CEp1CEp3

CEp7

CEp11

ADm26

ADm28

ADm30

ADm32

ADm34

CEm37

CEm47

WBCm55

WBCm56

WBCm57

WBCm64

WBCm66ADo72

ADo74

ADo78

ADo81RCo84

CEw84

RCo85

CEw85

CEw87

CEw88

CEw89

RCw93

RCw96 RCw99

CEa108

CEa114CEa116

BHHa120

RCw122

RCw126

RCw128

ADw130

ADw131

ADw132

ADw133

ADw134

ADw135

CEh143

CEh146

RCh152BHHh156

RCh158

ADh159GHh165GHh166

BHHh168

GIh170

SIh171

GHh181

SIh184

SIh186

ADh193

RCh195

GHh198

ADh208

ADh210

ADh212

GIn217

GIn219

GIn220

GIn227

CEn229

CEn231

CEn232

CEn236CEn241 WBCk245

WBCk251

WBCk255 WBCk257

ADu305

ADu308

ADu310

ADu312

ADu314

ADu318

CEu325

CEu328

CEu330

CEu332

CEu334

CEu335

SIu337

SIu338 SIu339

SIu340

SIu342

SIu343

SInL1N1

SInL2N2

BHHnL3N2

SInL4N1

SInL5N5

BHHnL6N4

SInL6N6

SInL7N7

PFBS

PFHxA

PFHxS

PFHpA

PFOS

PFOA

PFNA

PFDA

PFUnA

PFDoA

PFTrDA

PFTA

-3

-2

-1

0

1

2

3

-4 -3 -2 -1 0 1 2 3

F2 (

18

.12

%)

F1 (42.01 %)

Bird Species

CEp1CEp3

CEp7

CEp11

ADm26

ADm28

ADm30

ADm32

ADm34

CEm37

CEm47

WBCm55

WBCm56

WBCm57

WBCm64

WBCm66ADo72

ADo74

ADo78

ADo81RCo84

CEw84

RCo85

CEw85

CEw87

CEw88

CEw89

RCw93

RCw96 RCw99

CEa108

CEa114CEa116

BHHa120

RCw122

RCw126

RCw128

ADw130

ADw131

ADw132

ADw133

ADw134

ADw135

CEh143

CEh146

RCh152BHHh156

RCh158

ADh159GHh165GHh166

BHHh168

GIh170

SIh171

GHh181

SIh184

SIh186

ADh193

RCh195

GHh198

ADh208

ADh210

ADh212

GIn217

GIn219

GIn220

GIn227

CEn229

CEn231

CEn232

CEn236CEn241 WBCk245

WBCk251

WBCk255 WBCk257

ADu305

ADu308

ADu310

ADu312

ADu314

ADu318

CEu325

CEu328

CEu330

CEu332

CEu334

CEu335

SIu337

SIu338 SIu339

SIu340

SIu342

SIu343

SInL1N1

SInL2N2

BHHnL3N2

SInL4N1

SInL5N5

BHHnL6N4

SInL6N6

SInL7N7

PFBS

PFHxA

PFHxS

PFHpA

PFOS

PFOA

PFNA

PFDA

PFUnA

PFDoA

PFTrDA

PFTA

-3

-2

-1

0

1

2

3

-4 -3 -2 -1 0 1 2 3

F2 (

18

.12

%)

F1 (42.01 %)

Sites


References:Gebbink, W. A. et al., 2009. Environmental Science and Technology. 43(19):7443–7449.Holmström, K.E. & Berger, U. 2008. Environmental Science and Technology. 42(16):5879–84.Löfstrand, K. et al., 2008. Chemosphere. 72(10):1475–1480.Rüdel, H. et al., 2011. Environmental Science and Pollution Research. 18(9):1457–1470.Sedlak, M.D. & Greig, D.J. 2012. Journal of Environmental Monitoring. 14(1):146.Thompson, J. et al., 2011. Marine pollution bulletin. Elsevier Ltd. 62(12):2869–75.Verreault, J., Berger, U., & Gabrielsen, G.W. 2007. Environmental Science and Technology. 41:6671–6677.

Wang, Y et al., 2008 Environmental science & technology. 42(21):8146–51.


Figure 2: Global comparison of mean PFOS concentrations


Figure 2: Global comparison by feeding guild


Figure 3: Comparison between countries for PFOA, PFNA, PFUnA and PFDoA


Figure 4: Relative frequency of detection for PFCs (PFHxS, PFOA, PFNA, PFOS, PFUnA and PFDoA)

Range: 150 – 119 000 ng/g

Results and discussionSpecies Mean PFOS (ng/g) Maximum PFOS (ng/g)

African Darter 1100 2800

Reed Cormorant 550 2000

White-breasted Cormorant 370 670

Grey Heron 550 950

Cattle Egret 75 1000

Glossy Ibis 80 260

Black-headed Heron 130 730

Sacred Ibis 10 30

Results and discussionSpecies Mean PFOS (ng/g) Maximum PFOS (ng/g)

African Darter 1100 2800

Reed Cormorant 550 2000

White-breasted Cormorant 370 670

Grey Heron 550 950

Cattle Egret 75 1000

Glossy Ibis 80 260

Black-headed Heron 130 730

Sacred Ibis 10 30

+brominated flame

retardants, polychlorinated biphenyls and pesticides

References:Bouwman, H et al., 2014. Ecotoxicology and environmental safety. 104:393–402.Bouwman, H et al., 2015. Chemosphere. 126:1–10.Bouwman, H & Pieters, R. 2013. ORASECOMBouwman, H et al., 2008 Chemosphere. 71(2):227–41.Bouwman, H et al., 2013. Environmental Research. 126:240–253.Quinn, L.P. et al., 2013 Chemosphere. 90(3):1109–1116.

Conclusion

• PFBS and PFUnA detected in water

• PFOS and PFHxA detected in sediment

• PFHxA and PFOA detected in mine tailings

• No PFCs detected in fish

• Long chain PFCs were prevalent, with PFOS the dominant congener

• PFCs varied depending species and collection site. These differences could be attributed to multiple factors including diet, feeding habitat, area of sampling and differences in toxicokinetics

Conclusion

• In the Global comparison South Africa (SA) had the second highest mean PFOS concentration (398 ng/g)

• Comparing countries by feeding guild, SA had the highest piscivore mean PFOS concentration

• SA had the highest relative frequency of detection of PFCs in bird eggs

• PFCs are present in the South African environment, with high concentration levels found in bird eggs

• The combined toxicological effect of these chemical loadings on bird populations may be a cause for concern.

Acknowledgements

• Co-authors

• D Prevoo-Franzsen

• H Bouwman

• L Quinn

• Financial assistance provided by:

• South African Department of Trade and Industry

• United Nations Office for Project Services

• National Research Foundation of South Africa

• Organic and Bio-analysis group

• Photos provided by Henk Bouwman and Laura Quinn

perfluorinated compounds in water, sediment, and wild bird ......perfluorinated compounds in water,...

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