mylor, saltash and holes bay still show high levels of cu and zn and are highly polluted sites...

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Mylor, Saltash and Holes Bay still show high levels of Cu and Zn and are highly polluted sites compared to Tipner, Broadmarsh, Dell Quay and The Conservancy: Þ Cu and Zn are persistent ; Þ Metals are still a great concern in terms of water quality, risk management and ecotoxicological risk to marine life. Sediment organic content and grain size were correlated to metal bioavailability. Zn in pore water was more readily available than Cu to N. virens. N. virens did not accumulate metals directly from the sediment bioavailable fraction. N. virens may respond in a different way than N. diversicolor to metal pollution. • The King ragworm, Nereis virens, is an ecologically and commercially important polychaete species of soft sediment inter-tidal communities of the northern hemisphere and is known to be impacted by various anthropogenic activities. • Metals such as copper (Cu) and zinc (Zn) are naturally present in the ecosystem but can be found at high levels due to industrial activities and are known to be toxic to many marine invertebrates. • Aim: To investigate the relationships between metal bioavailable concentrations in the sediment, the pore water and the tissues of N. virens from sites with different pollution histories. The impact of site specific sediment characteristics on metal bioavailability and bioaccumulation in the polychaete Nereis virens Pini, J. M., Richir, J. and Watson, G. J. Institute of Marine Sciences, School of Biological Sciences, University of Portsmouth, UK Contact: [email protected] Weak but significant negative correlation Cu concentrations and worm weight => heavier worms accumulate less Cu in their tissues. No significant correlation between Zn concentrations and worm weight Introduction Results & Discussion Conclusion Samples processing Tissue metal concentrations and weight Site characteristics and metal bioavailability Table.1 Sediment characteristics and metal concentrations from the 7 sites sampled along the English Channel from summer 2011 to winter 2012. Silt particle size distribution determined using the statistical package Gradistat [2] are given in mean ± SEM. Cu and Zn concentrations (mean ± SEM, in mg kg -1 dry weight) were calculated using the BCR three-step sequential extraction. This procedure assesses the distribution of metals in the following fractions: exchangeable (i.e. water and acid soluble; step 1), reducible (i.e. iron/manganese oxides; step 2) and oxidisable (i.e. organic matter and sulphides; step 3). The sum of the 3 steps is described as the bioavailable concentration of Cu and Zn. All sites were characterised as very poorly sorted, very coarse skewed muddy sediment composed mainly of fine and very coarse silt. However, Mylor, Saltash and Holes Bay presented differences from Tipner, Broadmarsh, Dell Quay and The Conservancy in term of sediment characteristics , pollution history & metal bioavailable concentrations. Organic content for the sediment showed a modest but significant correlation with bioavailable Cu (r = 0.596; p = 0.004) and Zn (r = 0.658; p = 0.001) concentrations. Particle size showed a strong and significant correlation with both Cu (r = 0.791; p < 0.001) and Zn (r = 0.740; p < 0.001) bioavailable concentrations in the sediment. Fig.1 Map showing the location of the 7 sites sampled along the English Channel coast. 1) Mylor, Fal Estuary; 2) Saltash, Tamar Estuary; 3) Holes Bay, Poole Harbour; 4) Tipner, Portsmouth Harbour; 5) Broadmarsh, Langstone Harbour; 6) The Conservancy and 7) Dell Quay, Chichester Harbour. Materials & Methods Flame Atomic Absorption Spectroscopy (FAAS) BCR sequential extraction [1] Step 1. Acetic acid => Exchangeable phase Step 2. Hydroxylammonium chloride => Reducible phase Step 3. Hydrogen peroxide & ammonium acetate => Oxidisable phase Nitric acid extraction Sediment N. virens Pore water Organ ic conte nt & Parti cle size analy sis Sites Organic content (%) Silt particle size distribution (%) Cu bioavailabl e conc. Zn bioavailabl e conc. Very coarse (63-31 µm) Medium (31-8 µm) Fine (8-4µm) Very fine (4-2µm) Mylor 8.90 ± 0.35 40.92 ± 0.28 10.81 ± 0.10 37.37 ± 0.47 0.09 ± 0.00 421.83 ± 63.55 670.99 ± 46.00 Saltash 6.68 ± 0.48 33.85 ± 0.59 9.55 ± 0.24 46.94 ± 1.01 0.11 ± 0.00 87.84 ± 6.55 175.10 ± 23.79 Holes Bay 8.83 ± 0.18 28.75 ± 0.72 8.39 ± 0.38 54.34 ± 1.44 0.13 ± 0.00 47.99 ± 5.00 159.35 ± 30.97 Tipner 2.32 ± 0.19 26.29 ± 0.97 7.62 ± 0.06 58.34 ± 1.08 0.13 ± 0.00 23.35 ± 1.90 42.45 ± 9.25 Broadmarsh 5.20 ± 0.31 34.05 ± 1.01 11.00 ± 0.28 43.90 ± 1.54 0.10 ± 0.00 10.83 ± 0.57 36.43 ± 4.56 Conservanc y 3.96 ± 0.05 24.50 ± 1.35 7.78 ± 0.45 59.80 ± 2.24 0.14 ± 0.01 31.75 ± 1.41 54.02 ± 6.98 Dell Quay 3.28 ± 0.42 33.01 ± 0.80 9.28 ± 0.19 48.32 ± 1.16 0.11 ± 0.00 32.76 ± 2.98 41.75 ± 7.65 References [1] Pueyo, M., et al., 2001. Certification of the extractable contents of Cd, Cr, Cu, Ni, Pb and Zn in a freshwater sediment following a collaboratively tested and optimised three-step sequential extraction procedure. Journal of Environmental Monitoring. 3, 243-250. [2] Blott SJ, Pye K. 2001. GRADISTAT: A grain size distribution and statistics package for the analysis of unconsolidated sediments. Earth Surface Processes and Landforms 26: 1237-1248. Metal concentrations in tissues, sediment and pore water Site-specific Pearson’s correlation coefficients between N. virens individual Cu concentrations and weight revealed that only Saltash had a significant positive modest correlation (r = 0.585, p = 0.017). All other sites: weak, negative & non significant correlations (p > 0.05). 0 5 10 15 20 25 30 0 10 20 30 40 f(x) = − 0.361327474859019 x + 15.2618149480261 R² = 0.113335363254986 Individual worm (g) Cu (µg g-1 dw) 0 5 10 15 20 25 30 0 100 200 300 400 500 f(x) = − 2.05436398026853 x + 109.601790699883 R² = 0.0174099631805549 Individual worm (g) Zn (µg g-1 dw) Weak but significant negative correlation between Cu concentrations and worm weight: Þ Heavier worms accumulate less Cu in their tissues. No significant correlation between Zn concentrations and worm weight. Data for Zn revealed a mixture of positive (Saltash and Dell Quay) and negative correlations, but all were weak and non- significant (p > 0.05). Fig.2 Relationships between individual N. virens a) Cu or b) Zn concentrations and their respective wet weight. b) a) 0 50 100 150 200 250 300 350 400 450 500 0.0 0.5 1.0 1.5 2.0 f(x) = 0.00255484568295606 x + 0.849350264738979 R² = 0.730329520688675 Cu (mg kg -1 dw) in sediment Cu (µg L-1) 5 4 6&7 3 2 1 50 70 90 110 130 150 170 190 0.0 1.0 2.0 3.0 4.0 f(x) = 0.0201696344674594 x − 0.91721999113999 R² = 0.699598260825957 Zn (μg g -1 dw) in N. virens Zn (µg L-1) 5 2 4 3 7 6 Fig.3 Relationships between a) mean Cu concentrations in pore water and mean Cu bioavailable concentrations in sediment and between b) mean Zn concentrations in pore water and in N. virens. a) b) Cu concentrations in pore water and Cu bioavailable concentrations in sediment showed a significant and strong positive correlation. Zn concentrations in tissues and Zn concentrations in pore water had a significant and strong positive correlation. No correlation between Cu concentrations in tissues and Cu bioavailable concentrations in sediment (r = -0.054, p = 0.919) or Cu concentrations in pore water (r = -0.054, p = 0.958). No correlation between Zn bioavailable concentrations in sediment and Zn concentrations in pore water (r = 0.321, p = 0.482) or Zn concentrations in N. virens (r = -0.471, p = 0.346).

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Page 1: Mylor, Saltash and Holes Bay still show high levels of Cu and Zn and are highly polluted sites compared to Tipner, Broadmarsh, Dell Quay and The Conservancy:

Mylor, Saltash and Holes Bay still show high levels of Cu and Zn and are highly polluted sites compared to Tipner, Broadmarsh, Dell Quay and The Conservancy:Þ Cu and Zn are persistent ;Þ Metals are still a great concern in terms of water quality, risk management and ecotoxicological risk to marine life. Sediment organic content and grain size were correlated to metal bioavailability. Zn in pore water was more readily available than Cu to N. virens. N. virens did not accumulate metals directly from the sediment bioavailable fraction. N. virens may respond in a different way than N. diversicolor to metal pollution.

• The King ragworm, Nereis virens, is an ecologically and commercially important polychaete species of soft sediment inter-tidal communities of the northern hemisphere and is known to be impacted by various anthropogenic activities.

• Metals such as copper (Cu) and zinc (Zn) are naturally present in the ecosystem but can be found at high levels due to industrial activities and are known to be toxic to many marine invertebrates.

• Aim: To investigate the relationships between metal bioavailable concentrations in the sediment, the pore water and the tissues of N. virens from sites with different pollution histories.

The impact of site specific sediment characteristics on metal bioavailability and bioaccumulation in the

polychaete Nereis virensPini, J. M., Richir, J. and Watson, G. J.

Institute of Marine Sciences, School of Biological Sciences, University of Portsmouth, UKContact: [email protected]

Weak but significant negative correlation Cu concentrations and worm weight => heavier worms accumulate less Cu in their tissues. No significant correlation between Zn concentrations and worm weight

Introduction

Results & Discussion

Conclusion

Samples processing

Tissue metal concentrations and weight

Site characteristics and metal bioavailability Table.1 Sediment characteristics and metal concentrations from the 7 sites sampled along the English Channel from summer 2011 to winter 2012. Silt particle size distribution determined using the statistical package Gradistat [2] are given in mean ± SEM. Cu and Zn concentrations (mean ± SEM, in mg kg-1 dry weight) were calculated using the BCR three-step sequential extraction. This procedure assesses the distribution of metals in the following fractions: exchangeable (i.e. water and acid soluble; step 1), reducible (i.e. iron/manganese oxides; step 2) and oxidisable (i.e. organic matter and sulphides; step 3). The sum of the 3 steps is described as the bioavailable concentration of Cu and Zn.

All sites were characterised as very poorly sorted, very coarse skewed muddy sediment composed mainly of fine and very coarse silt.

However, Mylor, Saltash and Holes Bay presented differences from Tipner, Broadmarsh, Dell Quay and The Conservancy in term of sediment characteristics , pollution history & metal bioavailable concentrations.

Organic content for the sediment showed a modest but significant correlation with bioavailable Cu (r = 0.596; p = 0.004) and Zn (r = 0.658; p = 0.001) concentrations.

Particle size showed a strong and significant correlation with both Cu (r = 0.791; p < 0.001) and Zn (r = 0.740; p < 0.001) bioavailable concentrations in the sediment.

Fig.1 Map showing the location of the 7 sites sampled along the English Channel coast. 1) Mylor, Fal Estuary; 2) Saltash, Tamar Estuary; 3) Holes Bay, Poole Harbour; 4) Tipner, Portsmouth Harbour; 5) Broadmarsh, Langstone Harbour; 6) The Conservancy and 7) Dell Quay, Chichester Harbour.

Materials & Methods

Flame Atomic Absorption Spectroscopy (FAAS)

BCR sequential extraction [1]

Step 1. Acetic acid => Exchangeable

phase

Step 2. Hydroxylammonium chloride => Reducible phase

Step 3. Hydrogen peroxide & ammonium acetate

=> Oxidisable phase

Nitric acid

extraction

Sediment N. virens Pore water

Organic content

& Particle

sizeanalysis

SitesOrganiccontent

(%)

Silt particle size distribution (%) Cu bioavailable

conc.Zn bioavailable

conc. Very coarse(63-31 µm)

Medium(31-8 µm)

Fine (8-4µm)

Very fine(4-2µm)

Mylor 8.90 ± 0.35 40.92 ± 0.28 10.81 ± 0.10 37.37 ± 0.47 0.09 ± 0.00 421.83 ± 63.55 670.99 ± 46.00Saltash 6.68 ± 0.48 33.85 ± 0.59 9.55 ± 0.24 46.94 ± 1.01 0.11 ± 0.00 87.84 ± 6.55 175.10 ± 23.79

Holes Bay 8.83 ± 0.18 28.75 ± 0.72 8.39 ± 0.38 54.34 ± 1.44 0.13 ± 0.00 47.99 ± 5.00 159.35 ± 30.97Tipner 2.32 ± 0.19 26.29 ± 0.97 7.62 ± 0.06 58.34 ± 1.08 0.13 ± 0.00 23.35 ± 1.90 42.45 ± 9.25

Broadmarsh 5.20 ± 0.31 34.05 ± 1.01 11.00 ± 0.28 43.90 ± 1.54 0.10 ± 0.00 10.83 ± 0.57 36.43 ± 4.56Conservancy 3.96 ± 0.05 24.50 ± 1.35 7.78 ± 0.45 59.80 ± 2.24 0.14 ± 0.01 31.75 ± 1.41 54.02 ± 6.98

Dell Quay 3.28 ± 0.42 33.01 ± 0.80 9.28 ± 0.19 48.32 ± 1.16 0.11 ± 0.00 32.76 ± 2.98 41.75 ± 7.65

References[1] Pueyo, M., et al., 2001. Certification of the extractable contents of Cd, Cr, Cu, Ni, Pb and Zn in a freshwater sediment following a collaboratively tested and optimised three-step sequential extraction procedure. Journal of Environmental Monitoring. 3, 243-250.[2] Blott SJ, Pye K. 2001. GRADISTAT: A grain size distribution and statistics package for the analysis of unconsolidated sediments. Earth Surface Processes and Landforms 26: 1237-1248.

Metal concentrations in tissues, sediment and pore water

Site-specific Pearson’s correlation coefficients between N. virens individual Cuconcentrations and weight revealed that only Saltash had a significant positive modest correlation (r = 0.585, p = 0.017). All other sites: weak, negative & non significant correlations (p > 0.05).

0 5 10 15 20 25 3005

101520253035

f(x) = − 0.361327474859019 x + 15.2618149480261R² = 0.113335363254986

Individual worm (g)

Cu

(µg

g-1

dw)

0 5 10 15 20 25 300

100

200

300

400

500

f(x) = − 2.05436398026853 x + 109.601790699883R² = 0.0174099631805549

Individual worm (g)

Zn

(µg

g-1

dw)

Weak but significantnegative correlation between Cu concentrations and worm weight: Þ Heavier worms

accumulate less Cu in their tissues.

No significantcorrelation between Zn concentrations and worm weight.

Data for Zn revealed a mixture of positive (Saltash and Dell Quay) and negative correlations, but all were weak and non-significant (p > 0.05).

Fig.2 Relationships between individual N. virens a) Cu or b) Zn concentrations and their respective wet weight.

b)

a)

0 50 100 150 200 250 300 350 400 450 5000.0

0.5

1.0

1.5

2.0f(x) = 0.00255484568295606 x + 0.849350264738979R² = 0.730329520688676

Cu (mg kg -1 dw) in sediment

Cu (µ

g L-

1)

5 4

6&7

3

2 1

50 70 90 110 130 150 170 1900.0

1.0

2.0

3.0

4.0

f(x) = 0.0201696344674595 x − 0.917219991139991R² = 0.699598260825956

Zn (μg g -1 dw) in N. virens

Zn (µ

g L-

1)

5

2

43 7 6

Fig.3 Relationships between a) mean Cu concentrations in pore water and mean Cu bioavailable concentrations in sediment and between b) mean Zn concentrations in pore water and in N. virens.

a)

b)

Cu concentrations in porewater and Cu bioavailable concentrations in sediment showed a significant and strong positive correlation.

Zn concentrations in tissuesand Zn concentrations in pore water had a significant and strong positive correlation.

No correlation between Cu concentrations in tissues and Cu bioavailable concentrationsin sediment (r = -0.054, p = 0.919) or Cu concentrations in pore water (r = -0.054, p = 0.958).

No correlation between Zn bioavailable concentrations in sediment and Znconcentrations in pore water (r = 0.321, p = 0.482) or Zn concentrations in N. virens (r = -0.471, p = 0.346).