DETERMINATION OF BOOSTER BIOCIDES IN SEAWATER AND … · 2016. 5. 4. · 4. Sampling: Sediment EPA,...

Universidade Federal do Rio Grande – FURGEscola de Química e Alimentos – EQA

Programa de Pós-Graduação em Química Tecnológica e Ambiental - QTALaboratório de Análises de Compostos Orgânicos e Metais – LACOM

DETERMINATION OF BOOSTER BIOCIDES IN SEAWATER AND MARINE SEDIMENTS FROM

PANAMANIAN COASTAL AREAS:METHOD DEVELOPMENT AND SURVEY

JAHIR ANTONIO BATISTA ANDRADEAdviser: Prof. Ednei Gilberto Primel PhDCo-adviser: Prof. Gilberto Fillmann PhD

Rio Grande, 2016

1

Research line: Environmental Analytical Chemistry

2

GENERAL OBJETIVE• To determine booster biocides (Diuron, Irgarol, TCMTB, DCOIT

and dichlofluanid) in marine sediments and seawater fromPanamanian coastal areas applying vortex assisted MSPD and SPEtechnique accompanied with LC–MS/MS

SPECIFIC OBJECTIVES• To develop a SPE and a MSPD environmental friendly method for

determining five booster biocides in seawater and marinesediment;

• To validate these methods with SANCO parameters;• To collect samples in Panama;• To discuss the distribution of booster biocides in Panamanian

coastal areas;• To compare the results with other studies worldwide.

3

SUMARY

1. Introduction

2. Selected analytes

• Booster biocides

3. Materials and methods

• Solid Phase Extraction (SPE)

• Matrix Solid Phase Dispersion (MSPD)

• Liquid Chromatography coupled to mass spectrometric analysis (LC MS/MS)

4. Sampling

• Seawater

• Sediment

5. Results

• SPE optimization

• MSPD optimization

• SPE Validation

• Distribution of booster biocides in seawater from Panamanian coastal areas

6. Next steps

4

1. Introduction

Marine biofouling

DAFFORN, K. A.; LEWIS, J. A.; JOHNSTON, E. L. Antifouling strategies: history and regulation, ecological

impacts and mitigation. Marine Pollution Bulletin, v. 62, n. 3, p. 453-65, 2011.

Old wooden vessels

Antifouling painting

5

Compound

Effects Inhibition of photosynthesis in plantsCarcinogenic and deformed growth

in fish larvae

Log Kow 3.95 2.85

Molar mass 253.4 g mol-1 233.1 g mol-1

Vapor pressure 1.5 x 10-5 Pa 4.1 x 10-4 Pa

Boiling point 428.0°C 385.2°C

Water solubility 7.0 mg L-1 36.4 mg L-1

Table 1: Selected booster biocides for this study

ZHOU, J. L. Occurrence and persistence of antifouling biocide Irgarol 1051 and its main metabolite in the coastal waters of

Southern England. Science of The Total Environment, v. 406, n. 1–2, p. 239-246, 2008.

SAPOZHNIKOVA, Y. et al. Antifouling biocides in water and sediments from California marinas. Marine Pollution Bulletin, v.

69, n. 12, p. 189-194, 2013


6

Compound

EffectsInhibitor of the electron transport chain at the level of mitochondria

Carcinogenic and mutagenic effects in unicellular microorganisms

Log Kow 3.30 3.70

Molar mass 238.4 g mol-1 333.2 g mol-1

Vapor pressure 1.0 Pa 1.3 x 10-4 Pa

Boiling point NA 336.8°C

Water solubility 45 mg L-1 0.006 mg L-1

SAKKAS, V. A.; KONSTANTINOU, I. K.; ALBANIS, T. A. Photodegradation study of the antifouling booster biocide dichlofluanid in

aqueous media by gas chromatographic techniques. Journal of Chromatography A, v. 930, n. 1–2, p. 135-144, 2001.

HAMWIJK, C. et al. Monitoring of the booster biocide dichlofluanid in water and marine sediment of Greek marinas. Chemosphere,

v. 60, n. 9, p. 1316-1324, 2005.

MENESES, E. S.; ARGUELHO, M. L. P. M.; ALVES, J. P. H. Electroreduction of the antifouling agent TCMTB and its

electroanalytical determination in tannery wastewaters. Talanta, v. 67, n. 4, p. 682-685, 2005.

Table 1: Selected booster biocides for this study (cont.)


7

Compound

EffectsHigh microbial activity, especially with

bacteria, fungi and algae

Log Kow 2.85

Molar mass 213.3 g mol-1

Vapor pressure 4.0 x 10-4 Pa

Boiling point 322.6

Water solubility 0.0065 mg L-1

CASTRO, I. B.; WESTPHAL, E.; FILLMANN, G. Third generation antifouling paints: New biocides in the aquatic

environment. Quimica Nova, v. 34, n. 6, p. 1021-1031, 2011.

Table 1: Selected booster biocides for this study (cont.)


8

3. Methods


Reduce organic solvent

Reduce analysis time

Requires less manipulation

SPE provides higherconcentrations factors

Can be used to store analytes in a sorbed state

SPE refers to thenonequilibrium, exhaustiveremoval of chemicalconstituents from a flowingliquid sample via retention ona contained solid sorbent andsubsequent recovery ofselected constituents byelution from the sorbent.

WELLS, M. J. Principles of extraction and the extraction of semivolatile organics from liquids. Sample

Preparation Techniques in Analytical Chemistry, p. 37, 2003.

9

3. Methods


Figure 1: Four basic steps for solid-phase-extraction

CALDAS, S. S. et al. Modern techniques of sample preparation for pesticide residues determination in water by

liquid chromatography with detection by diode array and mass spectrometry. Quimica Nova, v. 34, n. 9, p. 1604-

1617, 2011.

10

3. Methods

SOUZA CALDAS, S. et al. A vortex-assisted MSPD method for the extraction of pesticide residues from fish liver

and crab hepatopancreas with determination by GC–MS. Talanta, v. 112, n. 0, p. 63-68, 2013

SEBASTIÀ, N. et al. Occurrence of aflatoxins in tigernuts and their beverages commercialized in Spain. Journal of

Agricultural and Food Chemistry, v. 58, n. 4, p. 2609-2612, 2010.

Recent modification to the original technique based on matrix solid-phasedispersion (MSPD) to determine pesticides in fish liver and crabhepatopancreas. VA-MSPD substitutes the SPE elution step with vortexagitation followed by centrifugation and further chromatographic analysis.

Figure 2: Vortex-assited MSPD adapated by Caldas et al, 2013


11

High recovery %

Short extraction times, low

cost.

One step for extraction

and cleaning

Small amounts of

sample

Small amounts of sorbent and

solvent

Biological tissues, soil, sludge, food

and sediments

Viability, flexibility, versatility

CALDAS, S. S. et al. Avanços recentes da MSPD para extração de resíduos de agrotóxicos, PPCPs,

compostos inorgânicos e organometálicos. Scientia Chromatographica, v. 5, n. 3, p. 190-213, 2013.

CAPRIOTTI, A. L. et al. Recent advances and developments in matrix solid-phase dispersion. TrAC Trends in

Analytical Chemistry, v. 71, p. 186-193, 2015.

3. Methods


12

Figure 3: Liquid chromatograph Alliance Separations Module 2695 (Waters, EUA), Detector MS,Micromass® Quatro Micro™ API (Waters, Inglaterra) API, electrospray ionization

3. Methods

13

4. Sampling

http://micanaldepanama.com/nosotros/

MONTERO LLÁCER, F. J. Panama Canal Management. Marine Policy, v. 29, n. 1, p. 25-37, 2005.

13 000 - 14 000 vessels/year38-40 vessels/day

Common shipping routes

14

4. Sampling

Figure 4: Samplingsites

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Identification Site Latitude (N) Longitude (W) Activities

PA01A Shelter Marina 1 09°21'58.00'' 79°57'04.10'' Recreational boats and shipyards (repair)

PA01B Shelter Marina 2

(Sea output)

09°21'55.20'' 79°57'00.25'' Open sea (way of the boats)

PA02 Colon port 09°21'54.49'' 79°53'40.49'' Container port and shipyards (repair)

PA03 Panama port 08°57'49.70'' 79°34'21.10'' Container port and small fishing boats

PA04 The Americas Bridge 08°56'43.20'' 79°33'54.90'' Entrance of Panama Canal-Pacific side

(way to the vessels)

PA05 La Playita Marina 08°54'33.50'' 79°31'37.60'' Marina, recreational boats, harbor and shipyards (repair)

PA06 Vacamonte port 08°51'44.50'' 79°40'22.60'' Fishing port

4. Sampling

Table 2: Sampling location information

16

Identification Site Latitude (N) Longitude (W) Activities

PA08 Flamenco marina 08°54'40.20'' 79°31'18.50'' Marina, recreational boats, harbor and shipyards (repair)

PA09 Seafood Market 08°57'30.78'' 79°32'09.41'' Fishing port, commercial and passengers jetty

PA10 Chiriqui Grande 10°38'29.30'' 85°39'00.30'' Oil tanks area, commercial and passengers jetty

PA11 Almirante 09°17'24.80'' 82°24'05.60'' Container port, commercial and passengers jetty

PA12 Bocas del Toro 09°20'12.20'' 82°14'34.70'' Recreational boats, commercial and passengers jetty

PA13 Puerto Armuelles 08°13'34.80'' 82°52'29.60'' Oil port and oil tanks area

4. Sampling

Table 2: Sampling location information (cont.)

17

4. Sampling: Sediment

EPA, U. S. Methods for Collection, Storage and Manipulation of Sediments for Chemical and Toxicological

Analyses: Technical Manual. EPA-823-B-01-002. U.S. Environmental Protection Agency, Office of Water.

Washington, DC. 2001.

ASTM. Standard Guide for Sampling Waste and Soils for Volatile Organic Compounds. ASTM D4547−09.

American Society for Testing and Materials (ASTM). West Conshohocken, United States. 2009

18


Materials:• Van Veen/Eckman grab• Aluminum containers

previously calcined (450 °Cfor 4 hours)

• Aluminum foil (alsocalcined)

• Latex gloves• Stainless steel spatula• Permanent markers, tape

and plastic bags

19


Recomendations:• Sediment samples should

preferably have agranulometry withpercentages of fines (clay andsilt) above 30%

• It is desirable that these becollected in places where thegranulometry is previouslyknown.

• These samples must betaking only the surface layer(2cm), representative ofrecent sediments.

• It must also be ruled out of thesample that is in direct contactwith the walls of the collectionteam.

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4. Sampling

Figure 5: Sample preparation steps

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4. Sampling

Figure 6: Samples ready for analysis

22

4. Sampling

Figure 7: Granulometry test

23

CompoundRetention time (min)

Quantification transition

(m/z)

Collision energy

(eV)

Confirmation transition

(m/z)

Collision energy

(eV)

Cone voltage

(V)

Diuron-d6* 4.20 239.33>78.1 17 239.33>52.1 15 29

Diuron 4.39 232.97>72 17 232.97>160 37 23

TCMTB 5.18 238.76>180 15 238.76>136 25 17

Irgarol 5.82 253.87>198 17 253.87>108 31 27

Dichlofluanid 5.98 332.82>123 29 332.82>76.9 57 23

DCOIT 7.84 281.91>170 15 281.97>57 17 29

Table 3: MRM conditions of mass spectrometry and retention time of the booster biocides. Positive ion (PI) mode (ESI +) and dwell time: 0.2 s

* Surrogate standard

5. Results

Chromatographic parameters

24

Diuron

TCMTB

Irgarol

Dichlofluanid

DCOIT

Figure 8: Multiple reaction monitoring (MRM) chromatograms for target analytes

5. Results

Chromatographic separation

25

MSPD for determining booster biocides in MARINE SEDIMENTS

5. Results

26

5. Results: MSPD optimization

Graphic 1: Effect of organic solvent on the extraction efficiency. Conditions: sample mass: 2 g;50 ng g-1 of each biocide in sediment sample; volume of organic solvent: 10 mL; macerationtime: 5 min; vortex time: 1 min; centrifugation time: 5 min

0

10

20

30

40

50

60

70

80

90

100

110

MeOH EtOH

% R

eco

very

Diuron

Irgarol

TCMTB

DCOIT

Dichlofluanid

R: 55 – 95 %RSD: < 11 %

R: 68 – 102 %RSD: < 4 %

aa

ab

b

aa

aa

a

27


0

10

20

30

40

50

60

70

80

90

100

110

120

10 mL EtOH 5 mL EtOH

%R

eco

very

Diuron

Irgarol

TCMTB

DCOIT

Dichlofluanid

Graphic 2: Effect of volume of ethanol on the extraction efficiency. Conditions: sample mass: 2g; 50 ng g-1 of each biocide in sediment sample; maceration time: 5 min; vortex time: 1 min;centrifugation time: 5 min.

R: 91 – 99 %RSD: < 20%

R: 86 – 96 %RSD: < 6%

a

a

a a

a

aa

a a a

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-20

-15

-10

-5

0

5

10

15

20

10 mL EtOH 5 mL EtOH

Diuron

Irgarol

TCMTB

DCOIT

Dichlofluanid

Graphic 3: Effect matrix of volume of organic solvent. Conditions: sample mass: 2 g; 50 ng g-1

of each biocide in sediment sample; maceration time: 5 min; vortex time: 1 min; centrifugationtime: 5 min.

ME: -5 to 10 % ME: -15 to 13 %

29


Optimal MSPD procedure

Sample mass: 2 gSolid support: 0.5 g C18Dispersion time: 5 minSolvent volume: 5 mL EtOH1 min vortex5 min centrifugationExtract ready for analysis

30

SPE for determining booster biocides in SEAWATER

5. Results

31

5. Results: SPE optimization

0

10

20

30

40

50

60

70

80

90

100

110

Strata C18-E Strata X Oasis®HBL

%R

eco

very Diuron

Irgarol

TCMTB

DCOIT

Dichlofluanid

Graphic 4: Effect of the type of cartridge on the extraction efficiency. Conditions: samplesolution: 250 mL; 10 µg L-1 of each biocide in water sample; volume of elution solvent: 2 mL

R: 55 – 95 %RSD: <15%

R: 7 – 93 %RSD: <8%

R: 2 – 47 %RSD: <14%

a

a a

aa

b

b

b

a

b

32

0

10

20

30

40

50

60

70

80

90

100

110

6,0 7,0 8,0

%R

eco

very

Sample pH

Diuron

Irgarol

TCMTB

DCOIT

Dichlofluanid


Graphic 4: Effect of sample pH on the extraction efficiency. Conditions: sample solution: 250mL; 10 µg L-1 of each biocide in water sample; cartridge: Strata C18-E; volume of elutionsolvent: 2 mL

R: 56 – 94 %RSD: <6%

R: 69 – 94 %RSD: <9%

R: 60 – 93 %RSD: <8%

a a a

b

aa,b

b

a a

b

a a

aa

b

33


Compound pKa

Irgarol 3.70

Diuron 4.12

TCMTB -----

DCOIT -----

Dichlofluanid -----

Table 4: pKa of compunds

Graphic 5: Species distribution of diuron as a function of pH values

DENG, J. et al. Multiwalled carbon nanotubes as adsorbents for removal of herbicide diuron from aqueous solution.

Chemical Engineering Journal, v. 193–194, p. 339-347, 2012.

BOLLMANN, U. E. et al. Polyacrylate–water partitioning of biocidal compounds: Enhancing the understanding of biocide

partitioning between render and water. Chemosphere, v. 119, p. 1021-1026, 2015.

SALEH, A.; SHEIJOONI FUMANI, N.; MOLAEI, S. Microfunnel-supported liquid-phase microextraction: Application to

extraction and determination of Irgarol 1051 and diuron in the Persian Gulf seawater samples. Journal of

Chromatography A, v. 1356, p. 32-37, 2014.

34


0

10

20

30

40

50

60

70

80

90

100

110

120

130

Salinity 10 Salinity 20 Salinity 30

% R

eco

very

Diuron

Irgarol

TCMTB

DCOIT

Dichlofluanid

R: 58 – 117 %RSD: < 4%

R: 59 – 112 %RSD: < 18%

R: 52 – 102 %RSD: < 19%

Graphic 6: Effect of sample salinity on the extraction efficiency. Conditions: sample solution:250 mL; 10 µg L-1 of each biocide in water sample; cartridge: Strata C18-E; volume of elutionsolvent (MeOH): 2 mL

a a

bab

ca a

b

a a

ba

a a

35


Optimal SPE procedure:

Sample volume: 250 mL pH= 7-8Salinity: 20 - 30Filtration: Sartorius cellulose acetate filter 0.45 µmCartridge: C18-E Conditioning: 6 mL MeOH + 6 mL milli-Q waterFlow rate: 10 mL min-1

Rinse: 1 mL milli-Q waterElution: 2 mL MeOH

Surrogate standard: 100 µL of 0.2 mg L-1

diuron-d6

Pre-concentrationfactor:

125x

36

5. Results: SPE validation

Limit of detection (LOD)

Limit of quantification (LOQ)

Linearity

Accuracy

Precision

Matrix effect

EUROPEN-COMMISSION. Guidance document on analytical quality control and validation procedures for

pesticide residues analysis in food and feed. SANCO/12571/2013, 2013, rev. 0. 386. 2013

37


Table 5: Method Limits of detection (LODm) and quantification (LOQm), calibration curvesprepared at solvent and at the extract, with their respective correlation coefficients (r).

AnalytesLODm

(ng L-1)LOQm

(ng L-1)

Calibration curves

Solvent r Extract r

Diuron 2.7 8.0 y=76387x+18.514 0.9995 y=89094x+20.253 0.9972

Irgarol 0.3 0.8 y=3x106x+213.42 0.9912 y=2.9x106x+248.33 0.9973

TCMTB 13.3 40 y=214771x+175.67 0.9993 y=210633x+4.362 0.9989

DCOIT 1.3 4.0 y=67582x+28.643 0.9968 y=83255x+2.8077 0.9978

Dichlofluanid 2.7 8.0 y=36935x+31.468 0.9991 y=34378x+28.054 0.9937

38


Table 6: Accuracy (R), precision (RSDr and RSDip), and matrix effect (ME)

Analytes

R (%) RSDr (%) RSDip (%) ME (%)

LOQ 5LOQ10LO

QLOQ 5LOQ

10LOQ

LOQ 5LOQ LOQ 5LOQ 10LOQ

Diuron 106 111 117 12 9 2 6 10 -1 -2 -7

Irgarol 130 83 112 3 12 6 7 15 -11 2 -3

TCMTB 89 81 88 10 8 15 11 13 1 -8 -10

DCOIT 113 88 88 13 8 5 2 7 5 -3 -1

Dichlofluanid 92 83 75 9 7 1 8 10 7 -2 5

39

ANTIFOULING BOOSTER BIOCIDES IN SEAWATER FROM COASTAL AREAS OF

PANAMA: First data in one of the world’s busiest

shipping zones

5. Results

40

5. Results: Distribution of booster biocides in seawater

Identification SiteDiuron (ng L-1) ± RSD

(%)

Irgarol (ng L-1) ±

RSD (%)

PA01A Shelter Marina 1 36 ± 9 5 ± 6

PA01BShelter Marina 2

(Sea output)<LOQ <LOQ

PA02 Colon port <LOQ <LOQ

PA08 Flamenco marina 70 ± 6 2 ± 8

Table 7: Concentration of antifouling biocides found in seawater samples taken from Panamanian coastal areas

41


0

10

20

30

40

50

60

70

80

90

100

110

120

130

Re

cove

irs

(%)

%R: 78 to 120 %RSD : < 13 %

Graphic 7: Recoveries of Diuron-d6 in real samples from Panama. Conditions: samplesolution: 250 mL; 100 µL of 0.2 mg L-1 of diuron-d6 in seawater sample; sample pH: 7-8;salinity: 20-30; cartridge: Strata C18-E; volume of elution solvent: 2 mL

42


PA01A: Shelter Marina36 ng L-1 Diuron5 ng L-1 Irgarol

43


PA01A: Shelter Marina36 ng L-1 Diuron5 ng L-1 Irgarol

a) Standard Irgarol 0.005 mg L-1

b) Sample PA01A

Figure 9: MRM of a) Irgarol standard in solvent at 0.005 mg L-1 and b) real sample PA01A

44


PA01B: Shelter Marina (Output sea)<LOQ Diuron<LOQ Irgarol

45


PA02: Colon<LOQ Diuron<LOQ Irgarol

46


PA08: Flamenco Marina70 ng L-1 Diuron

2 ng L-1 Irgarol

47


PA08: Flamenco Marina70 ng L-1 Diuron2 ng L-1 Irgarol

a) Standard Diuron 0.01 mg L-1

b) Sample PA08

Figure 10: MRM of a) Diuron standard in solvent at 0.005 mg L-1 and b) real sample PA08

48


LogKow: 3.30Sw: 45 mg L-1

LogKow: 2.85Sw: 0.0065 mg L-1

• It extremely stable complexes withsediments.

• Rapid degradation (less than a fewdays) and have a short half-life (ina few hours) in water andsediment

LogKow: 3.70Sw: 0.006 mg L-1

• Hydrolytic half-life inseawater (pH 8.2, 20°C): 1.2 h

• Photolysis half-life inseawater by naturalsolar irradiation: 53 h

HAMWIJK, C. et al. Monitoring of the booster biocide dichlofluanid in water and marine sediment of Greek marinas.

Chemosphere, v. 60, n. 9, p. 1316-1324, 2005.

SAKKAS, V. A.; KONSTANTINOU, I. K.; ALBANIS, T. A. Photodegradation study of the antifouling booster biocide

dichlofluanid in aqueous media by gas chromatographic techniques. Journal of Chromatography A, v. 930, n. 1–2, p. 135-

144, 2001.

MENESES, E. S.; ARGUELHO, M. L. P. M.; ALVES, J. P. H. Electroreduction of the antifouling agent TCMTB and its

electroanalytical determination in tannery wastewaters. Talanta, v. 67, n. 4, p. 682-685, 2005.

49


What we know about theother sampling sites?

Tributyltin (TBT)

Triphenyltin (TPT)

Penis in females

Are they still using TBT paints?

Imposex in gastropods Picture by: Ítalo Braga Castro

50


Are these levels harmful tothe marine ecosystem? UK, Sweden and

Denmark restricted Irgarol use on boats <25

m in length

Dutch National Institute of Public Health and the Environment: 430 ng L-1

for Diuron and 24 ng L-1

for Irgarol

Climatic factorsConsider partitioning,

persistence andbioavailability

These data demonstrate the use of these compounds in

antifouling paints

ZHOU, J. L. Occurrence and persistence of antifouling biocide Irgarol 1051 and its main metabolite in the coastal

waters of Southern England. Science of The Total Environment, v. 406, n. 1–2, p. 239-246, 2008.

LAMOREE, M. et al. Determination of diuron and the antifouling paint biocide Irgarol 1051 in Dutch marinas and

coastal waters. Journal of Chromatography A, v. 970, n. 1, p. 183-190, 2002.

51


Table 8: Comparison of antifouling biocide concentrations (ng L -1) found in water in this study with other reported studies.

Location, year AnalysisIrgarol (ng L -1)

Diuron (ng L -1)

Other biocides(ng L -1)

Reference

Greece, 2000SPE GC-ECD

GC-FTD11 - 90 -----

DCOIT: 49Dichlofluanid: 24 –284Chlorothalonil: 63-31

(SAKKAS et al., 2002)

Netherlands, 2000

SPE LC-MS/MS 9 - 90 90 - 1130 -----(LAMOREE et al.,

2002)

Denmark, 2004 SPE GC-MS ----- ----- DCOIT: 283(STEEN et al.,

2004)

Puerto Rico and the US Virgin Islands, 2006

SPE GC-MS 1 - 1300 ----- -----(CARBERY et al.,

2006)

SouthernEngland, UK,

2008SPE GC-MS <3.1 - 89 ----- M1: <0.5 – 30 (ZHOU, 2008)

Gran Canaria, Spain, 2011

SPE LC-MS/MS 2.4 - 146 2.3 - 203TCMTB: nd

Dichlofluanid: nd

(SÁNCHEZ-RODRÍGUEZ et al.,

2011)

Panama, 2016 SPE LC-MS/MS <1 – 5 <8 – 70DCOIT: ndTCMTB: nd

Dichlofluanid: ndThis study

52


Table 8: Comparison of antifouling biocide concentrations (ng L -1) found in water in this study with other reported studies (cont).

Location, year AnalysisIrgarol (ng L -1)

Diuron (ng L -1)

Other biocides(ng L -1)

Reference

São Luiz, Maranhão, Brasil,

2011SPE LC-MS/MS 20 – 4800 50 – 7800 -----

(DINIZ et al., 2014)

Malaysia, 2013 SPE LC-MS/MS 5 – 2021 1 – 285 -----(ALI et al.,

2013)(ALI et al., 2014)

California, USA, 2013

SPE LC-MS/MS 254 68 M1: 62(SAPOZHNIKOVA

et al., 2013)Bushelr, Iran,

2013MF-LPMEHPLC-UV

11 – 63 29 3,4-DCA: 47 – 289(SALEH et al.,

2015)

Seto Inland Sea, Japan, 2014

SPE HPLC-UV 3 31 -----(KAONGA et al.,

2016)

Rio Grande, Brazil, 2014

SPE LC-MS/MS 6 21 -----(DOMINGUEZ et

al., 2014)

South Korea, 2014

LLE LC-MS/MS 14 35 – 1360DCOIT: nd

Zn/Cu pyrithione: nd(KIM et al., 2014)

Panama, 2016 SPE LC-MS/MS <1 – 5 <8 – 70DCOIT: ndTCMTB: nd

Dichlofluanid: ndThis study

53

References

• SAKKAS, V. A. et al. Survey for the occurrence of antifouling paint booster biocides in

the aquatic environment of Greece. Environmental Science and Pollution Research,

v. 9, n. 5, p. 327-332, 2002.

• LAMOREE, M. et al. Determination of diuron and the antifouling paint biocide Irgarol

1051 in Dutch marinas and coastal waters. Journal of Chromatography A, v. 970, n. 1,

p. 183-190, 2002.

• STEEN, R. J. C. A. et al. Monitoring and evaluation of the environmental dissipation of

the marine antifoulant 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT) in a Danish

Harbor. Chemosphere, v. 57, n. 6, p. 513-521, 2004.

• CARBERY, K. et al. Contamination of Caribbean coastal waters by the antifouling

herbicide Irgarol 1051. Marine Pollution Bulletin, v. 52, n. 6, p. 635-644, 2006.

• ZHOU, J. L. Occurrence and persistence of antifouling biocide Irgarol 1051 and its main

metabolite in the coastal waters of Southern England. Science of The Total

Environment, v. 406, n. 1–2, p. 239-246, 2008.

• SÁNCHEZ-RODRÍGUEZ, Á. et al. Probabilistic risk assessment of common booster

biocides in surface waters of the harbours of Gran Canaria (Spain). Marine Pollution

Bulletin, v. 62, n. 5, p. 985-991, 2011.

• DINIZ, L. G. R. et al. First appraisal of water contamination by antifouling booster

biocide of 3rd generation at Itaqui Harbor (São Luiz-Maranhão-Brazil). Journal of the

Brazilian Chemical Society, v. 25, n. 2, p. 380-388, 2014.

• ALI, H. R. et al. Occurrence and distribution of antifouling biocide Irgarol-1051 in coastal

waters of Peninsular Malaysia. Marine Pollution Bulletin, v. 70, n. 1–2, p. 253-257,

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References

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6. NEXT STEPS

Freeze drysedimentsamples

Sedimentcharacterization

MSPD validationMSPD in samples

from Panama

Dissertation

PPCPs in sediment

samples of theAmericas

56

ACKNOWLEDGEMENTS

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