Flotation chemicals and biological observations in sediment at the sea deposit site in Frænfjorden

Hilde C. Trannum & Carlos Escudero Senior Research Scientists, NIVA

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Outline

- Introduction- Chemical characteristics- Biological characteristics

- Epifauna/infauna- Structure/function

- Research highlights

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Ramirez-Llodra et al., 2015. Marine Pollution Bulletin 97: 13-35.

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Frænfjorden• Møre og Romsdal county • 12 km long with a maximum depth of around 70 m • Tidal range about 2 m and the fjord is well flushed• Recipient for Omya Hustadmarmor AS, discharge from Tine

meierier, municipal water and runoff from agriculture

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Frænfjorden sea deposit• Sea deposit from 1982• ~ 300 k tons/year in the last years • The discharge takes place at 20 m depth, and the tailings

are deposited in a basin at 40-70 m depth • As a result of the discharge, the depth of the fjord in

certain areas has gradually decreased by up to 25 m from the original depth

• Tailings:• 40–50 % calcium carbonate• Fine grained: ~ 97% < 63 µm, 30% < 4 µm• No elevated levels of metals• Process chemicals; flocculation chemicals (anionic polyacrylamide) and cationic flotation chemicals

• Sediment close to the discharge > 99% fine fraction (< 63 µm)

NY1

NY8NY7

NY6NY5

NY4NY3 NY2

Frænfjorden chemical field stationsFrænfjorden sediment chemistry stations

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Gemini coresSampling depth: four fractions

1. 0-1 cm2. 1-3 cm3. 3-5 cm4. 5-10 cm

Frænfjorden chemistry sampling

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- Flotation reagent FLOT2015 employed in Hustadsmarmor.

- Cationic tensioactive, family of Esterquats

- Mixture of different chemical structures

+H3C

O–

O

n

Hydrolysis

Fatty acid.Environmentally non-relevant

Sediments and pore water from Frænfjordenanalyzed for:

- Identification of the different components of the raw material (including the QAC core).

- Identification and Quantification of the QAC core (standard available).- Screening to tentatively identify the presence of transformationproducts

QAC core; final expected product ofthe degradation of theflotation chemical

The analyses were performed at the Institute for Energy Technoloy (IFE) using Ultra High Performance Liquid Chromatography coupled to High Resolution Mass Spectrometry

(UPLC-HRMS; Orbitrap).

Suspected substances in the tailings from Hustadsmarmor

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RT: 0.00 - 13.15 SM: 7G

0 1 2 3 4 5 6 7 8 9 10 11 12 13Time (min)

0

20

40

60

80

100

Rel

ativ

e A

bund

ance

0

20

40

60

80

100

Rel

ativ

e A

bund

ance

0

20

40

60

80

100

Rel

ativ

e A

bund

ance

9.97

8.76

7.63 11.868.838.667.52 9.07 11.7210.83 11.957.33 12.316.98 9.255.22

5.01 7.26 7.935.53 8.766.424.87 10.29 11.029.370.64 11.98 13.122.83 3.42 3.9511.04

8.63

11.168.33 8.69 9.928.297.42 10.967.31 11.818.95 12.406.816.66 9.85

NL: 1.59E5m/z= 428.37130-428.37558 F: FTMS + p ESI Full ms [100.00-1000.00] MS Sample-66

NL: 7.56E6m/z= 306.18945-306.19251 F: FTMS + p ESI Full ms [100.00-1000.00] MS Sample-66

NL: 1.64E5m/z= 414.35571-414.35985 F: FTMS + p ESI Full ms [100.00-1000.00] MS Sample-66

O

ON

+OH

OH

H3C

CH3

C-11 monoester

Tentative. Transf. Product from 428

O

ON

+OH

OH

H3C

H3C

C-10 monoester

We have tentatively identified so far:

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Screening of the raw chemical and transformation products in sediments

E:\xcalibur\...\Sample-60 08/31/16 01:05:38

RT: 0.05 - 10.21 SM: 7B

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 10.0Time (min)

0

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Rel

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1.15

1.53 1.69 1.93 2.18 2.42 4.134.022.67 2.98 3.25 3.50 4.33 4.55 5.50 9.76 10.111.06 5.14 6.40 7.63 8.225.64 7.414.99 6.16 9.368.906.55 8.398.086.85 7.14

NL: 6.07E7m/z= 164.12730-164.12894 F: FTMS + p ESI Full ms [100.00-1000.00] MS Sample-60

Sample-60 #103 RT: 1.20 AV: 1 NL: 7.69E6T: FTMS + p ESI Full ms [100.00-1000.00]

163.0 163.2 163.4 163.6 163.8 164.0 164.2 164.4 164.6 164.8 165.0 165.2 165.4 165.6 165.8m/z

0

10

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Rel

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164.12854C7 H18 O3 N

165.13191165.47792162.96631 163.96461

163.07570C10 H11 O2

165.02597C4 H7 O6 N

HO

N+

OH

OH

H3C

QAC core. The main transformation product.

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Screening of the raw chemical and transformation products in Frænfjorden

NY1

NY8

Y6NY5NY4

NY3 NY2

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QAC profile in sediments from the fjord: distance from the pipe and depth

NY1

NY8

Y6NY5NY4

NY3 NY20 2 4 6 8 10 12 14

0-1

1-3

3-5

5-10

C QAC (microg/L)

Dept

h (c

m)

St. NY1

0 20 40 60 80 100 120 140

0-1

1-3

3-5

5-10

C QAC (microg/L)

Dept

h (c

m)

St. NY3

0 10 20 30 40 50

0-1

1-3

3-5

5-10

C QAC (microg/L)

Dept

h (c

m)

St. NY4

0 10 20 30 40 50 60 70

0-1

1-3

3-5

5-10

C QAC (microg/L)

Dept

h (c

m)

St. NY5

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QAC profile in sediment porewater: distance from the pipe and depth

• The cationic tensioactive FLOT2015 undergoes hydrolytic degradation once dischargedinto the fjord.

• The products of the likely degradation route (QAC and fatty acids) are considered asnon-toxic and with low bioaccumulation potential. However, there is still presence oftensioactive in living organisms exposed to the tailings (mussels and sea cucumbers).

• A fraction of the product remains adsorbed to the particles of the tailing and anotherdissolves into the surrounding water

• In overall, FLOT2015 can be considered as an evolution of the industrial tensioactivesfollowing a concept of “Benign by design”. The product has been chemically designedwith “water-sensitive” bonds with the objective of fading out in the water environmentwith relatively low long-term impact.

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Research highlights: chemistry

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Frænfjorden: State of benthic communities in situInfauna Epifauna

Infauna-data 2013-2016 (DNV & NIVA)Epifauna 2016 (NIVA)

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Infauna Epifauna

Giant sea cucumber(‘rødpølse’): 1.06 kg ww.

Benthic univariate responses

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Multivariate patternInfauna Epifauna

Tailings gradient Tailings gradient

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0,1 m2: 50-100 species>1000 individuals

NutrientsCarbon

Contaminants

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From structure to function

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Trait Code Features/ modalities

Activity Adult life habit AH 1 2 3 4 5 6

Sessile Permanent tube Semi-permanent tube Burrower Surface crawler Swimmer

Degree of attachment DA 1 2 3

None Temporary Permanent

Adult mobility (relative) AM 1 2 3 4

None Low Medium High

Sediment dwelling depth SD 1 2 3 4 5

0 cm (surface) 0-1 cm 1-5 cm 5-15 cm > 15 cm

Faecal deposition FD 1 2 3

Sediment surface Subsurface 0-5 cm Deep subsurface > 5 cm

Size and shape Body form BF 1 2 3 4 5 6

Short cylindric Flattened dorsally Flattened laterally Ball-shaped Long, thin threadlike Irregular

Normal adult size NS 1 2 3 4 5 6

< 0.5 cm 0.5-1 cm 1-3 cm 3-6 cm 6-10 cm > 10 cm

Life history Feeding FH 1 2 3 4 5 6 7 8 9

Suspension/ filter feeder Surface deposit feeder Subsurface deposit feeder Deep deposit feeder Dissolved matter/ symbionts Sandlicker/ large detritus/ scraper Scavenger Carnivore/ omnivore Parasite/ commensal

Life duration LD 1 2 3

< 1 year 1-5 years > 5 years

Reproduction No of reprod/ year NY 1 2 3

< 1 1 2 or more

Reprod period RP 1 2 3 4 5

Winter (December-February) Spring (March-May) Summer (June-August) Autumn (September-November) no particular season

Reprod technique RT 1 2 3 4

Asexual (budding) Broadcast spawner Dermersal eggs Brooder, viviparous

Larvae type LT 1 2

Planktotroph (feeding larvae) Lecitotroph (non-feeding larvae)

Bioturbatory activity

Sediment reworking SR 1 2 3 4 5 6

Surface living/ epifauna Surficial modifier Upward conveyor Downward conveyor Biodiffusor Regenerator

Traits-analysis: rationale

What the species do rather than the taxonomic identity

• Traits analysis describe ecosystem functions• Describe the diversity of functions in species

assemblages (“functional diversity”)

Functional attributesFeedingSize and shapeActivity

Life habitat/positionMobilityFaecal depositionSediment reworking

ReproductionLarvae typeReproduction techniqueReproduction period

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Infauna Epifauna

Tailings gradient Tailings gradient

Functional responses

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Functional diversity

EpifaunaInfauna

Improved status due to replacement of chemical from Lilaflot to FLOT2015?

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Ecological classification

All stations obtained at least «good» condition(> class II) !

Infauna 2016

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IMPACT MECHANISMS

• Hypersedimentation• Particle properties (freshly grinded, fine-

grained, homogenous) • Reduced oxygen penetration (fatty acids)• Toxicity

• (Metals from the ore)• Process chemicals; flotation chemicals (and flocculation chemicals)

In combination?

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Research highlights: benthos

• Epifauna responded stronger than infauna• Traits-analysis points out which ecological

functions are most sensitive to the mine tailings

• Functional diversity a novel tool to quantifythe functional responses of a disturbance

• Impact mechanisms complex

• Include epifauna in benthic monitoring? A monitoring including the most vulnerable ecosystem compartment would also be according to precautionary principle

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FURTHER READING

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Questions ?

Thank you !