lc-tandem ms strategies for the analysis of contaminants of emerging concern in water ... ·...

LC-Tandem MS Strategies for the Analysis of Contaminants of Emerging Concern in Water,

Soil and Sediment Samples

Damià Barceló, Bozo Zonja, Marina Gorga, Marta Llorca, Josep Sanchís,

Marinel.la Farré, Sandra Pérez, Mira Petrovic, Sara Rodriguez-Mozaz

New Developments in the Analysis of Complex Environmental Matrices

http://www.sep-sci.org.uk/index.html

Outline

Determination of endocrine disruptors and related compounds in river and

wastewaters by Equan followed by LC-tandem MS 1

3

On-line system Turboflow (TFC) coupled to an UHPLC-Orbitrap MS system for the clean up of tetracycline after enzymatic degradation of contaminated waters

2

4 Q-Eactive Orbitrap MS with atmospheric pressure photionization interface (APPI) for the analysis of fullerenes in several environmental matrices

Detection-based prioritisation of phototransformation products of Iodinated contrast media in surface waters

Conclusions 5

Determination of endocrine disruptors and related

compounds in river and wastewaters by Equan followed by LC-tandem MS

Marina Gorga, Mira Petrovic and Damià Barceló

Natural and synthetic estrogens and

conjugates

Estradiol (E2)

Estriol (E3)

Estrone (E1)

Ethinyl estradiol (EE2)

Diethylstilbestrol (DES)

Estrone 3-sulfate (E1-3S)

Estriol 3-sulfate (E3-3S)

Estrone 3-glucuronide (E1-3G)

Estriol 16-glucuronide (E3-16G)

Estradiol 17-glucuronide (E2-17G)

Endocrine Disruptors and related Compounds (EDCs)

Anticorrosives

1H-Benzotriazole (BT)

Tolytriazol (TT)

Antimicrobials

Triclosan (TCS)

Triclorocaraban (TCC)

Preservatives

Methylparaben (MeP)

Ethylparaben (EtP)

Propylparaben (PrP)

Benzylparaben (BeP)

Plasticizer

Bisphenol A (BPA)

Alkylphenolic compounds

Octylphenol (OP)

Nonylphenol (NP)

Octylphenol Monocarboxylate(OP1EC)

Nonylphenol monocarboxylate (NP1EC)

Octylphenol monoethoxylate (OP1EO)

Nonylphenol monoethoxylate (NP1EO)

Octylphenol diethoxylate (OP2EO)

Nonylphenol diethoxylate (NP2EO)

Organophosphorus compounds

Tris(cloroisopropyl) phosphate (TCCP)

Tris(2-cloroetyl) phosphate (TCEP)

Tris(butoxietyl) phosphate (TBEP)

Endocrine disruptors compounds (EDCs) are a group of exogenous substance that

interfere with the endocrine system and disrupt the physiological function of hormones.

EDCs can act in a low dose in a variety of organisms producing developing disorders such

as sexual development problems, feminizing of males or masculine effects on females,

infertility …

Some of these contaminants are found in a high variety of products commonly used in the

daily life

Preconcentration Column

Triple Quadrupole

TSQ Vantage System Thermo Scientific

with Aria TLX-1 software

Analytical Column 6-Port

Valve

Large Loop

(1ml-5ml)

Eluting

Pump

Loading

Pump

Analysis of EDCs in water using dual column LC switching system (EQuan – LC-MS/MS)

Analyze high number of compounds for sample (multiresidual)

Compounds with different properties

injection volumes: 2-5 ml

Waste

Loading

Pump

Eluting

Pump

Pre

concentr

ation

Colu

mn

Analytical

Column

MS

Preconcentration

1-3 mL/min

0,3 mL/min Waste

Loading

Pump

Eluting

Pump

Pre

concentr

ation

Colu

mn

Analytical

Column

MS

Analysis

1-3 ml/min

0,3 mL/min)

EQuanTM technology. Signal Suppression effects

Effluent waste water

4.0 4.5 5.0 5.5 6.0 Time (min)

2000

40

60

80

100

2000

40

60

80

100

4.0 4.5 5.0 5.5 6.0

Intensity

271>183

271>183

Estradiol

A

B Intensity

Estradiol

Reconstructed ion chromatograms of MS/MS (271>183) corresponding to [M-H]- of estradiol obtained under NI conditions of spiked samples at level concentration of 250 ng/L. A) offline SPE-LC-MS/MS; B) online LC-LC-MS/MS

Llobregat

Júcar

Ebro

Guadalquivir

Llobregat: 14 sampling points

Ebro: 24 sampling points

Júcar: 15 sampling points

Guadalquivir: 24 sampling points

Total: 77 sampling points

Total river and sediments samples during 2

campaigns: 308 samples

2 campaigns (river water and sediments)

EDCs in Iberian rivers

LLO1

LLO2 CAR1

C

A

R

2

CAR3

ANO1 LLO3 LLO4

LLO5 ANO2 CAR4

LLO6 LLO7

ANO3

Llobregat River

d

Receive the

impact of

agricultural activity

LLO3 and ANO1

Receive the impact of a

big city and/or industrial

activity

LLO4 and ANO2

Upstream of a WWTP

CAR2 and LLO5

Downstream of a WWTP

CAR3, CAR4, ANO3 and LLO6

The end of the river

LLO7

Near to river source

LLO1 and LLO2

Reference site:

CAR1

Sampling points

Sediment samples

Co

nce

ntr

atio

n in n

g/g

River samples

Con

ce

ntr

atio

n in n

g/L

Anticorrosives Organophosphorus flame retardants Alkylphenolic compounds

NP OP

BPA Preservatives Antimicrobials/Disinfectants

Natural and synthetic estrogens and conjugates

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2

LLO1 LLO2 LLO3 CAR1 CAR2 CAR3 CAR4 LLO4 LLO5 ANO1 ANO2 ANO3 LLO6 LLO7

100

200

300

400

500

600

700

800

900

1000

C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2 C1 C2

LLO1 LLO2 LLO3 CAR1 CAR2 CAR3 CAR4 LLO4 LLO5 ANO1 ANO2 ANO3 LLO6 LLO7

0

On-line system Turboflow (TFC) coupled to an UHPLC-Orbitrap MS system for the clean up of tetracycline after enzymatic degradation of contaminated waters

Marta Llorca, Sara Rodríguez-Mozaz and Damià Barceló

Main objectives

To develop a screening method for the investigation of any possible transformation product (TP) by on-line turbulent flow chromatography coupled to LC-(ESI)-LTQ Orbitrap.

Study of Tetracycline TPs generated during enzymatic treatment by LTQ-Orbitrap. Work done in collaboration with the Institute Européen des Membranes from Montpellier (M. de Cazes, M.-P. Belleville, E. Petit, J. Sanchez) under the frame of the ENETECH project.

1

2

Chromatograph: Aria TLX-1 system (Thermo Fisher Scientific)

Analyzer: LTQ Orbitrap Velos (Thermo Fisher Scientific)

Turbulence on-line extraction and purification

Turbulent flow chromatography coupled to LTQ-Orbitrap

LC column TFC column

Chromatograph Analyzers Ionization source

Turbulent flow on-line extraction and purification

Characteristics

Turbulence flow : 1.5 – 3.0 ml/min

Columns poor size > 5 µm

Sample extraction in turbulent flow

Remove matrix sample

Retention of analyte in activated pore sites

(due to the difference between diffusion of big

and small compounds)

Turbulent flow

Turboflow principles

Large particle columns (30 µm or larger)

High flow rate, low back pressure

Efficient mass transfer created by turbulence

Elimination of large molecules; peptides, proteins

Capture of small molecules

LTQ-Orbitrap mass spectrometry analysis: 2 acquisition modes

1) Full Scan mode:

By Orbitrap

Rs = 60,000

m/z range = 100 – 1000

ESI = Positive and Negative ionization mode

2) Data dependant scan:

By Ion Trap

Minimum signal intensity: 100

MS2 fragmentation of the 5 most intense peaks from the full scan

(from 200 – 700)

1) Sample analysis by TFC-(ESI)-LTQ-Orbitrap

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0

Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Re

lati

ve A

bu

nd

ance

3.19

3.39

3.25

3.45

4.03

t = 0h

t = 20h

No TPs can be identified

TIC of tetracycline samples at 0 h and 20 h of degradation treatment. Analysis through direct injection of the samples

Direct injection

TIC F: FTMS + p ESI Full ms [400.00-500.00] MS Resolution 60000

TIC of tetracycline samples at 0 h and 20 h of degradation treatment. Analysis after off-line SPE clean-up step

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0

Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rela

tiv

e A

bu

nd

an

ce

3.09

3.09

3.86 3.41

t = 0h

t = 20h

TPs

Off-line SPE


0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0

Time (min)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

Re

lati

ve

Ab

un

da

nc

e


TIC of tetracycline samples at 0 h and 20 h of degradation treatment. Analysis through on-line TFC

0 1 2 3 4 5 6 7 8 9

Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rela

tive A

bu

nd

an

ce

2.48

2.57

6.62

2.47

2.56

6.60

7.38

t = 0h

t = 20h TPs


On-line TFC

0 1 2 3 4 5 6 7 8 9

Time (min)

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

8.0

8.5

9.0

9.5

10.0

Re

lati

ve

Ab

un

da

nc

e


2) Postulated Tranformation Products during degradation treatment

OH O OH O O

NH2

OH

OH

NHOm/z= 461.15546 Error = 1.06 ppm Ratio formation = 2.3

m/z= 459.1398 Error = 0.611 ppm Ratio formation = 6.9

m/z= 443.1449 Error = -0.632 ppm Ratio formation = 12.2

m/z= 416.0976 Error = 1.203 ppm Ratio formation = 39

m/z= 398.0870 Error = 1.006 ppm Ratio formation = 5.8

m/z= 382.0921 Error = -0.805 ppm Ratio formation = 2.0 m/z= 367.0812

Error = -1.268 ppm Ratio formation = 13.1

m/z= 323.0914 Error = 0.755ppm Ratio formation = 2.1

m/z= 397.0918 Error = 0.838ppm Ratio formation = 55.5

Hydroxylation

Dehydrogenation

Dehydrogenation

or

C4 oxidation

Water elimination

Water elimination

Water elimination

Oxytetracycline

Dehydrooxytetracycline

Methacycline 12-dehydrotetracycline

3,6,10,12a-tetrahydroxy-6-methyl-

1,4,11,12-tetraoxo-

1,4,4a,5,5a,6,11,11a,12,12a-

decahydrotetracene-2-carboxamide

4-dedimethylamino-4-oxo-

anhydrotetracycline

4-hydroxy-6-

methylpretetramide 2-Decarboxytetrangomycin

(-)-tetrangomycin

{4,5-Dihydroxy-3-[(1Z)-1-

hydroxy-3-oxo-1-penten-1-

yl]-9,10-dioxo-9,10-dihydro-

2-anthracenyl}acetic acid

Tetracycline

OH O OH O O

NH2

OH

OH

NOH OH

OH O OH O O

NH2

OH

OH

NOH O

OH O O O O

NH2

OH

OH

NOH

OH O O O O

NH2

OH

OH

NOH

OH O O O O

NH2

OH

OH

OOH

OH OH O O O

NH2

OH

OH

O

OH OH OH OH O

NH2

OH

OH

OH O

O

O

OHO

OH

OH O

O

OOH

OH O OH OH O

OH

O

O

Detection-based prioritisation of Iodinated contrast media phototransformation products in surface water

Bozo Zonja, Sandra Perez and Damià Barceló

Iodinated X-ray Contrast Media (ICM)

• ICM are used to improve the visibility of blood vessels in X-

ray radiography

• metabolically stable, short half life

• most intensively used compounds – 50-100 g per

diagnosis

• Frequently detected in wastewaters at µg/L levels, and up

to 0.1µg/L in surface waters

• Water/wastewater disinfection can lead to a formation of highly toxic iodinated

disinfection by-products (DBPs) from non-toxic ICM

Simulation of Environmental Processes

Photodegradation in Xenon Test Instrument (Suntest,

Heraeus) using auxiliary filters for simulation of natural

sunlight

Irradiation of test solution containing drug in quartz vials

Dark controls

http://upload.wikimedia.org/wikipedia/commons/4/4c/Solar_Spectrum.png

Photolysis of related compounds

Iohexol (IOX) Iopromide (IOP)

TPs detected in photolysis samples

I

OH

I

OHN

OH

HO

O

N

O

O

NHHO

OH

C19H26I2N3O9+

Exact Mass: 693.9753

Mol. Wt.: 694.2328

I

I

OHN

OH

HO

O

NH

O

NHHO

OH

C16H22I2N3O7+


Mol. Wt.: 622.1702

I

OH

I

OHN

OH

HO

O

N

O

OH

O

NHHO

OH

C19H26I2N3O10+


Mol. Wt.: 710.2322

I

I

I

OHN

OH

HO

NH OH

OH

O

NHHO

OH

C17H25I3N3O8+

Exact Mass: 779.877

Mol. Wt.: 780.1086

O

N

I

I

I

O

NH

OH

HO

O

HN

OH

HO

HO

OH

IOHEXOL

I

I

I

OHN

OH

HO

NH OH

OH

O

H2N

C14H19I3N3O6+


Mol. Wt.: 706.03

I

I

OHN

OH

HO

O

N

O

O

NHHO

OH

C18H24I2N3O8+


Mol. Wt.: 664.2069

I

I

OHN

OH

HO

O

N

O

NHHO

O

OH

O

C18H22I2N3O9+

Exact Mass: 677.944

Mol. Wt.: 678.1904

I

I

OHN

OH

HO

O

N

O

O

NHHO

O

C19H24I2N3O8+


Mol. Wt.: 676.2176

I

I

OHN

OH

HO

O

N

O

NO

OH

OH

OH

C18H22I2N3O9+

Exact Mass: 677.944

Mol. Wt.: 678.1904

I

I

OHN

OH

HO

O

N

OH

O

NO

OH

C19H24I2N3O8+


Mol. Wt.: 676.2176

I

OHN

OH

HO

O

N

O

OH

O

NHHO

OH

HO

OH

C19H27IN3O11+


Mol. Wt.: 600.3351

I

OHN

OH

HO

O

N

O

O

NHHO

OH

HO

OH

C18H25IN3O10+


Mol. Wt.: 570.3091

I

OHN

OH

HO

NH O

O

O

NHHO

OH

HO

OH

C17H23IN3O10+


Mol. Wt.: 556.2825

I

OHN

OH

HO

NH O

O

O

NHO

HO

OH

C17H21IN3O9+


Mol. Wt.: 538.2673

6 parent compounds

108 transformation products

SIEVE 2.0: generation of TPs list and screening of

photodegradation samples: example - iodixanol

TARGET SUSPECT NON-

TARGET

ANALYSIS ANALYSIS /

SCREENING SCREENING

TARGET

SUSPECT

NON-

TARGET

We know the compound, we have the standard,

Analytical method optimised (typically low resolution MS)

We know/suspect the compound, we don’t have the standard,

Analysis/Screening method optimised in comparison to similar

Compounds (typically high resolution MS)

We don’t know the compound, we don’t have the standard,

Screening as general as possible (large range of properties) (typically high resolution MS)

Introduction – Analytical method of choice?

Detection of TPs in real samples: methodology

13 surface water samples from Catalonia

7 from Llobregat river

6 from Besos river

Detection of TPs in real samples: methodology

• SPE cartridges

Oasis HLB, Bond Elut PPL, Oasis MAX and Oasis

MCX connected in series

• Extraction

800 mL of sample loading at 10 mL/min; drying with N2

• Elution

HLB & PPL: 3x3 mL of methanol/ethyl acetate (1:1)

MAX: (1) 3x3 mL of methanol/ethyl acetate (1:1)

(2) 2x3 mL of 2% HCOOH in methanol

MCX: (1) 3x3 mL of methanol/ethyl acetate (1:1)

(2) 5% of NH3 in methanol

• UPLC

Waters ACQUITY BEH C18 column (100 × 2.1 mm, 1.7

m)

Gradient elution: ACN:0.1% HCOOH ,10:90 90:10

• (+)ESI-MS (Q Exactive-MS)

Full-scan at RSP of 100 000 (m/z 400); 1 Hz

MS data processing – Thermo Xcalibur and Sieve

Prioritized TPs by their frequency of detection

in surface waters

Isolation of TPs by semi-preparative LC

Semipreparative

C18 column

6 photo

TPS

Isolation

of the standards

Identification of the TPs

with Q-Exactive

hv

Iodixanol TP747 -91 -18 -128 601.9278

MS2 of m/z 747.9

Confirmation with 13C/1H-NMR spectroscopy

In summary

0 2000 4000 6000 8000 10000

1

2

3

4

5

6

7

1

2

3

4

5

6

concentration in ng/L

Bulk concentration of allPARENT ICM

Bulk concentration of all ICMPHOTOTRANSFORMATIONproducts

Besos river

Llobregat river

Quantitative analysis of surface water samples by

Q-Exactive-MS

Sam

pli

ng

po

ints

Q-Exactive Orbitrap MS with atmospheric pressure photoionization interface (APPI) for the analysis of fullerenes in several environmental matrices: suspended materials of wastewater and river water, soils and sediments

Josep Sanchís, Marinel.la Farré and Damià Barceló

Fullerenes are carbon allotropes in a hollow spherical shape which have

recently attracted attention because of their interesting properties and

applications.

They are regarded as “carbon-cage” nanomaterials with certain number of

carbon atoms.

Fullerenes aggregate in the environment creating nano-sized aggregates.

Environmental and toxicological concerns have raised about the release of

fullerenes and other nanomaterials New emerging pollutants.

Properties: regio-aromatic (not super-aromatic), insoluble in water and organic

solvents of commun use in laboratories, soluble in toluene, thermo-stable, non-

volatile, bactericide…

Fullerenes: a new class of emerging pollutants

NATURAL EVENTS

Volcanism

Forest fires

Meteorite impacts

INCIDENTAL EMISSION NANOTECHNOLOGY

Combustion-related

processes.

Industrial processes.

Traffic emissions.

Several real and potential

applications

Sources of fullerenes

Advantages of APPI over ESI:

• Better sensitivity - ~100 times better than ESI.

• Better spectra - adducts are virtually inexistent.

• Less matrix effect.

130325-011 #523-547 RT: 9.12-9.42 AV: 13 NL: 1.83E6F: FTMS - p ESI Full ms [100.00-1300.00]

650 700 750 800 850 900 950

wavelength (nm)

0

100000

200000

300000

400000

500000

600000

700000

800000

900000

1000000

1100000

1200000

1300000

1400000

1500000

1600000

1700000

1800000

Inte

nsity

843.04433

737.00099

859.03868

719.99991 751.01810

875.03403783.00785

891.03001827.05074653.06587 693.05848984.31422929.05479

[12C60].-

[12C60OH].-

[13C112C59O].-

[12C60O].-

[12C60-CH3OH].-

[12C60O-CH3OH].-

[12C60O2-Tol].-

[12C60O3-Tol].-

[12C60O4-Tol].-

ESI APPI

[12C60].-

APPI analysis of fullerenes

The matrix effect is reduced with APPI, especially in complex extracts (soils, wastewater, river sediments and air particulate).

0

20

40

60

80

100

TolueneBlank

GroundWater

Tap Water Sea Water WastewaterInfluent

Sand RiverSediment

Soil Krill AirParticulate

Ins

tru

me

nta

l s

ign

al

(%)

C60 (C18-ESI(-)-Q-Orbitrap-MS) C70 (C18-ESI(-)-Q-Orbitrap-MS)

C60 (Buckyprep-APPI(-)-Q-Orbitrap-MS) C70 (Buckyprep-APPI(-)-Q-Orbitrap-MS)

APPI analysis of fullerenes

13C60

HPLC

DETECTION

Q-Exactive

APPI (-)

Fullscan

QUANTIFICATION

Water

filtration Drying

PREPARATION

Ultrasound

Particulate

Rotavap.

extraction

Centrifug.

Isotope dilution with

Liquid fraction

Evaporation

Liquid-liquid ext.

N2(g) flow

• Column:

Buckyprep column

• Mobile phase:

Toluene 100%

(0.4 mL/min)

• Stationary phase:

Pyrenylpropyl

Bonded silica

Method for the analysis of fullerenes in water

12 effluents of WWTPs.

26 freshwater samples from the Llobregat and Besòs

rivers.

To assess the impact of WWTPs in receiving

environments, the river samples were collected ~1

km downstream and upstream of WWTPs discharge

points

0

1000

2000

3000

4000

5000

6000

MONTCADAOUT

ST.FELIU OUT MANRESAOUT

RUBI OUT RIU-SEC OUT MONTCADAOUT

pg/L

C60

C70

WASTEWATER EFFLUENTS

Analysis of freshwater and wastewater samples from Catalonia

1

10

100

1000

10000

BE

S1

BE

S2

BE

S3

BE

S4

BE

S5

BE

S6

LL

OB

1

LL

OB

2

LL

OB

3

LL

OB

4

LL

OB

5

LL

OB

6

LL

OB

7

Co

ncen

trati

on

(p

g/L

) C60C70

RIVER SAMPLES

Results in river water particulate (Ø>450 nm)

There is not a clear relationship between concentrations in river water and the

discharge of nearby wastewater effluents.

Other inputs must be also considered (for instance, atmospheric deposition).

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

40 240 440 640 840 1040

Aggregate size (nm)

NTA Graphene nano-powder suspension

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

40 240 440 640 840 1040

Aggregate size (nm)

Nano-Au suspension Nanoparticle Tracking Analysis (NTA) detects

and visualises populations of nanoparticles in

liquids down to 10nm, and measures the size of

each particle from direct observations of diffusion.

This particle-by-particle methodology goes

beyond traditional light scattering and other

ensemble techniques in providing high-resolution

particle size distributions

Nanoparticle Tracking Analysis (NTA)

J. Sanchís, C. Bosch, M. Farré, D. Barceló. Analytical and Bioanalytical Chemistry (2014) Accepted

NTA characterization of water samples

a

a: blank

b: river water

c: ww effluent

d: ww influent

Nanoparticles in the water samples were characterized:

NPs concentration and size distribution.

b

c d


NTA characterization of water samples: CONCENTRATION


Conc. ranking: Wastewater influents > Wastewater effluent ≥ River water

Concentrations ranged between 106 and 109 nanoparticles/ml.

Discharges from wastewater effluents do not alter significantly the concentrations in

river water.

NTA characterization of water samples: SIZE

Size ranking: Wastewater influents < Wastewater effluent < River water

Nanoparticle sizes increases during the WWTP treatment

Nanoparticles sizes increases in lower ionic strength medium

Smaller nanoparticles present are associated to higher risk


51 soil and sediment samples from Santa Catarina state

(Brazil).

46 soils (rural and urban).

11 sediments.

Ultrasound assisted extraction carried out with toluene.

Analysis of soils and sediments from Brazil.

11 URBAN SOILS

Located near the largest coal-fired

thermoelectric power station in South

America.

Mostly, ricefields and meadows.

From coastal municipalities in Sul

Catarinense: Imbituba, Tubarão, Treze de Maio

and Jaguarana.

35 RURAL SOILS

0

5

10

15

20

25

30

35

40S

1

S3

S5

S7

S9

S11

S13

S15

S17

S19

S21

S23

S25

S27

S2

9

S31

S33

S35

S37

S39

S41

S43

S45

pg/g

Agricultural soils

C60 (pg/g)

C70 (pg/g)

Urban soils

55

C60 and C70 were detected in most of the samples (91% of urban samples)

In rural soils: Average concentration of C60: 6.22 pg/g. C70:1.77

In urban soils: Average concentration of C60: 23.8 pg/g. C70:15.0

Concentrations of fullerenes in Brazilian soils.

100 pg/g 154 pg/g

0

10

20

30

40

50

�S

ED

01

�S

ED

02

�S

ED

03

�S

ED

04

�S

ED

05

�S

ED

06

�S

ED

07

�S

ED

08

�S

ED

09

�S

ED

10

�S

ED

11

�S

ED

12

�S

ED

13

�S

ED

14

�S

ED

15

pg/g

C60 C70

Fullerenes in Sediments from Tubarao River (Brazil)

• C60 and C70 were detected in most of the samples (93% of sediments).

• Mean concentration of C60: 8.46 pg/g (67% of positives).

• Mean concentration of C70: 17.8 pg/g (93% of positives).

Analysis of Brazilian river sediments

Some considerations about Fullerene aggregation and Humic A. Interactions

with non polar contaminants, pH influence and sorption

Fullerene can be suspended in water as fullerene-aggregates. Extremely

hydrofobic with a tendency to aggregate and deposit in polar solvents due to

strong van der Waals forces. Hydrophobic and π-π interactions primary

mechanisms

FulvicA-nC60 complex accounted for 22.7 % of total nC60 containing

10mg/L of FA. Association KnC60-FA increased at pH 3-5 (F Wu et al, Environ

Pollut, 2013)

Humic/FulvicA decreased freely dissolved PAHs concentration on the

PAHs-nC60 (Hu.X et al, Environ Toxic Chem 2008)

Aging of fullerenes (e.g., exposure to sunlight, oxidation) results in a reduced

sorption affinity and capacity with non-polar contaminants /Thilo Hofmann,

E,S & T, 2013)

Adsorption of ATRAZINE by aqueous dispersion of nC60 increases with

lower pH. HA reduces size of C60, increases adsorption . Gai et al, E,S &T,

2011

Engineered CNT show stronger sorption capacity for herbicides than soils,

sediments and biochar (K Sun, Stoten, 2012)

Conclusions o The use of a dual column LC system for EDC with a six port valve reduced the interferences,

and improved the analysis parameters obtaining an enhanced optimization.

o Screening method was developed for the investigation of any possible transformation products (TPs) by on-line turbulent flow chromatography coupled to LC-(ESI)-LTQ Orbitrap.

o Several transformation products (TPs) of Tetracycline generated during enzymatic treatment with Laccase from Trametes versicolor were characterised and identified with LTQ-Orbitrap-MS

o The major advantages of the detection-based suspect screening of TPs in environmental

samples are; o a) generation of potential, environmentally relevant TPs under controlled laboratory

conditions o b) rapid HR-MS-based screening of environmental samples for the presence of these

TPs with high confidence o c) accelerated quantitative method development as compared to conventional QqQ-

MS-based analysis as no compound-specific MS parameters need to be optimized o The use of APPI over ESI for determination of nanomaterials showed better sensitivity –

(~100 times better than ESI) as well as better spectra (adducts are virtually inexistent) and less matrix effect.

Acknowledgments

EU FP7 project Marie Curie ITN CSI: Environment

PITN-GA-2010-264329

IDAEA-CSIC team ICRA teamº

EU FP7 project ENDETECH (FP7-ENV-2011-ECO-INNOVATION)

Managing the effects of multiple stressors on aquatic ecosystems

under water scarcity

(FP7-ENV.2013.6.2-1– Grant Agreement no 60362)

SCIENCE OF THE TOTAL ENVIRONMENT

VIRTUAL SPECIAL ISSUE THIS VIRTUAL SPECIAL ISSUE is a comprehensive

selection of articles published in Science of the Total

Environment during the last two years. It covers major

issues regarding the problems associated with pesticides

in the environment such as occurrence and fate in surface

waters, wastewaters groundwater contamination,

bioaccumulation, human health impacts and effects on

biota in the aquatic environment. The VSI also covers

water treatment for pesticide removal and soil degradation

studies.

ALL ARTICLES ARE FREE TO ACCESS ONLINE.

VISIT THE JOURNAL HOMEPAGE FOR DETAILS:

www.elsevier.com/locate/stoten

PESTICIDES IN THE ENVIRONMENT

COMPILED BY:

Damia Barcelo Barcelona and Girona,

Spain

Jim Bennett Madison Wisconsin, USA

IMPACT FACTOR

OF SCIENCE OF THE

TOTAL

ENVIRONMENT:

3.258

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