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Summarized Jurnal Asignment IV

by:
Gani Asa Dudin (437107402)

Superfisor:
Prof. Dr. Ali Al Homaidan

DEPARTMENT BOTANY AND MICROBIOLOGY

KING SAUD UNIVERSITY
RIYADH
2017
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1. Introduction
There has been a significant reduction in industrial discharges into the local estuaries
and coastal waters in northeast of England. Urbanised indus¬trial centres grew mainly
around the estuaries of the Tyne River, the Wear River, and the Tees River (Fig. 1).
Domestic sewage, previously discharged untreated into the rivers, has been largely
diverted to treatment plants located on or near the coast.

Fig. 1. Map of the northeast of England and sampling sites.

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The aim of this work was to find out whether changes in economic development and
recent cleanup measures have produced an improvement in environmental conditions in the
marine environment. The main objective was an assessment of the present heavy metal
concentration in sediments and in the brown alga Fucus vesiculosus.
Estuaries and coastal areas are thus the largest repositories of contaminants. Detritus-
feeding organisms are directly exposed to sediment-bound metals. Many workers have
assessed environmental conditions and metal bioavailability by means of biomonitors such
as seaweed and mussels.
There is evidence of seasonal variations of trace metal concentration in macroalgae
(Bryan and Hummerstone, 1973; Fuge and James, 1973, 1974; Young, 1975), especially
for Mn, Fe, Zn, Cu, Cd, Co, and Al. The general trend appears to be an increase in
concentraution in the winter and early spring, and minimum concentrations in the
summer and autumn.
Samples of mussels from Tees mouth and Holy Island have been analysed during a
survey of the UK coastline of the North Sea (Widdows et al., 1995), but there is limited
published information on heavy metals in seaweed from the stretch of coastline comprised
between the Wear River and the Tees River. Also, the author is not aware of any published
report on combined studies of local biomonitors and sediments.
This paper reports the trace metal concentrations in the seaweed F. vesiculosus and in
sediments from coastal sites of northeast England. The data on seaweed are also compared
with information about the common mussel Mytilus edulis obtained in a parallel
investigation (Giusti et al., 1999).

2. Materials and methods

a. Sampling Methods Materials And Methods
Seaweed samples were collected during the winter 1997-1998 from the upper to
middle tidal area at 17 sites (Fig. 1): Roker North Pier, Roker estuary, Easington,
Horden, Blackhall Rocks, Middleton, North Gare, five sites at Bran Sands, and four
sites at Holy Island. Holy Island was chosen as a control location as the main activities
on this island are fishing and tourism, and because it is situated off the coast of a rural
part of Northumberland.
At each site, a composite sample of seaweed was obtained by combining the most
recent 8-10 cm of fronds removed from 20-30 randomly chosen plants.
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If typical growth rates of 2-3 cm month-1 are assumed (Knight and Parke, 1950),
the samples collected in this study would give an integrated concentration of heavy
metals for a time span of about 3-5 months. The seaweed was cleaned in the field as
much as possible with marinewater, placed in polyethylene bags containing seawater
from the local environment, and taken to the laboratory after a few hours.
Intertidal surface (top 5 cm) sediments were collected at eight of the above sites,
namely:At each site, three samples were taken within an area of about 10 m2. They
were removed with a polyethylene scoop and immediately wet-sieved with marine
water to separate the pelite (< 63 µm) and the fine-grained sand (more than 63 pm to
less than 180 µm). Large detritus was separated by sieving through 2- mm sieves.
Additional samples were sieved to determine the sediment grain size distribution.
1) Seawed (Fucus vesiculosus)
Fucus vesiculosus, known by the common name bladder wrack or
bladderwrack, is a seaweed found on the coasts of the North Sea, the western
Baltic Sea, and the Atlantic and Pacific Oceans, also known by the common names
black tang, rockweed, bladder fucus, sea oak, black tany, cut weed, dyers fucus,
red fucus, and rock wrack
Kingdom : Plantare
Superphylum :Heterokonta
Class : Phaeophyceae
Order : Fucales
Family : Fucaceae
Genus : Fucus
Species : F. vesiculosus
Binomial name : Fucus vesiculosus
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Picture 2: Fucus vesiculosus

(http://www.alamy.com/stock-photo/fucus-vesiculosus.html
https://alexhyde.photoshelter.com/image/I0000KwjNctYCfmE)

2) Blue Mussel (Mytilus edulis)

The blue mussel (Mytilus edulis), also known as the common mussel, is a
medium-sized edible marine bivalve mollusc in the family Mytilidae, the mussels.
Blue mussels are subject to commercial use and intensive aquaculture.
Kingdom : Animalia
Phylum : Mollusca
Class : Bivalvia
Subclass : Pteriomorphia
Order : Mytiloida
Family : Mytilidae
Subfamily : Mytilinae
Genus : Mytilus
Species : M. edulis
Binomial name: Mytilus edulis (Linnaeus, 1758)
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Picture3: Mytilus edulis

http://www.marlin.ac.uk/species/detail/1421
http://www.marinelifephotography.com/marine/mollusks/bivalves/mytilus-edulis-
complex.htm
http://www.centralcoastbiodiversity.org/pacific-blue-mussel-bull-mytilus-trossulus.html

b. Analytical methods
1) Seaweed
The seaweed was briefly washed with deionised water, dried at 105°C for 48
h, cooled, weighed, and ashed at 475°C in a muffle furnace for 24 h (Fuge and
James, 1973). From each sample, three 5-g aliquots of the ashed material were kept
in 50-ml glass beakers with 20 ml aqua regia (5 ml of 16 M HNO3 and 15 ml of 16
M HCl) for 48 h. They were later refluxed on a hot plate, and diluted to 50 ml with
deionised water.
2) Sediment
Sediments were dried in the oven at 1050C for 48 h. Three aliquots of 1 g of
each dry sediment fraction were separated. The sediment aliquots were prepared
for digestion by grinding them to a fine powder with an agate mortar and pestle,
and ashed at 4750C in a muffle furnace for 2 h.
The method of standard addition was used to correct for matrix effects. Salt
matrix effects for Ag, Cd, Ni, Pb, and Cu were overcome by using matrix
modifiers.
All digest solutions were analysed, at least in duplicate, by flame atomic
absorption spectrophotometry (Varian SpectrAA-10Plus) and by graphite furnace
atomic absorption spectrophotometry (Varian SpectrAA-300 with GTA96 graphite
tube atomiser). Metals analysed included Fe, Mn, Zn, Cu, Pb, Ni, Cr, Cd, and Ag.
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3) Quality control
The precision and recovery of the procedures were checked using the
following certified standard reference materials: NIES No. 9 Sargasso seaweed,
GBW07302 stream sediment, GBW07313 marine sediment, and SRM2711
Montana soil.
No correction was applied to our data. Replicate analyses gave coefficients of
variation of less than 5% for all elements except Cr, Cd, and Ag for which
variations were up to 11 %.

3. Results and discussion

a. Seaweed
The most abundant elements found in the seaweed material analysed are Fe, Mn,
Zn, and Cu, and the least. The concentration sequence of the most abundant elements
is usually Fe > Mn > Zn > Cu. However, at Holy Island, Mn> Fe, and at Whitburn,
Roker, Easington, Blackhall Rock, and one site at Bran Sands Zn>Mn.
The highest Mn enrichment in seaweed is at Holy Island (276-778 mg kg -1),
which is also characterised by the lowest concentrations of Zn (13-18 mg kg -1), Pb
(0.1-1.1 mg kg -1), and Ni (0.3-0.7 mg kg -1).At Bran Sands, Fe and Mn enrichment in
seaweed decreases sig¬nificantly from Sites 13 to 17, going downstream along the
southern part of the Tees estuary.
The possibility that seaweeds may have been contami¬nated with metals
scavenged by iron oxyhydroxides present in fine sediment particles was considered
and tested in two ways: (1) assuming that all the iron in the seaweed samples
originated from sediment contamination, and (2) comparing metal/Fe ratios in
sediment and seaweed. Potential contam¬ination from sediment particles appears
theoretically possi¬ble only for Pb.
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b. Sediment
Observations with a binocular microscope revealed that the sediments were
largely composed of quartz, carbonates, and feldspars, some coated by oxides, and
mixed with shell debris. Opaque minerals (mostly pyrite) were present. Coal particles
were also common in all sediments. Very small grains could not be identified.
In general, these authors found that the seabed sediments of Tyneside and
Teesside were above these background values. Even though a direct comparison with
our data cannot be made due to the different size range of the sediment fraction
analysed, these values can be referred to as baseline concentrations.
The organic matter content (as % LOI) in sediments is generally in the range 0.4-
3.6%. The relatively higher percentage found at Easington, Horden, North Gare,
andespecially at Blackhall Rocks are partly due to the presence of small particles of
coal, especially in the sand fraction.
Copper shows the highest positive correlation with % LOI (r=.901, P<.01) in the
fine-grained sand (Fig. 7 and Tables 6 and 7).Other metals positively correlated with
organic matter in the sand fraction are Fe, Zn (both at P<.01), Pb, and Ni (both at P <
.05).
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c. Comparison between heavy metal concentrations in sediments and marine

organisms
The aqua regia-extracted Zn, Cu, and Pb in sediments are positively correlated
(P<.05) with those of F. vesiculosus, as shown for example in Fig. 8 for Zn. A sig-
nificant correlation (P<.05) was also found for Ni extracted from the sand fraction.
These relationships indicate that some of the metals held in the sediment may become
available to the seaweeds.

d. Metal pollution index (MPI)

Lower MPI in algal material is to be expected, as accumulated heavy metals
derive only from dissolved species present in marine water. Sediments are normally
larger repositories of contaminants.However, the variations in algal MPI between sites
appear to be similar, though of a different order of magnitude, to the variations of
sediment (fine sand) MPI. Fig. 9 shows that the two sets of MPI are significantly
correlated (r=.959, n=8). The correlation between pelite MPI and algal MPI (n = 6) is
not significant.
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e. Comparison between heavy metal concentrations in seaweeds and mussels

Along the coastline studied, the concentration of Cu, Zn, Pb, Cd, and Ag in
seaweed is usually lower than in soft tissue of mussels (Giusti et al., 1999) from the
same sites. Only at Roker was the Zn accumulated by F. vesiculosus higher than in M.
edulis. Nickel is more abundant inseaweeds than in mussels from Holy Island, Roker,
and Blackhall Rocks, and Cr levels are higher in seaweeds at Holy Island and
Middleton.
High levels of Mn or Zn in water are known to suppress the accumulation of trace
amounts of dissolved Cd, Co, Ni, Zn, or Mn in seaweed as a result of competition for
available binding sites
It is thus possible that the low Zn, Ni, and Cd values in seaweeds at Holy Island
might be caused by the high accumulation of Mn. Also, the general lack of a
significant correlation between Mn and any of the other metals analysed in seaweed
may be partially due to the same reason.

4. Conclusions
a. Seaweeds from Whitburn, Roker, Easington, and Horden, have a relatively high
burden of Zn (511-1016 mg kg -1), Cu (23-51 mg kg -1), Cr (3.0-5.0 mg kg -1), and, at
the latter three sites, of Ni (20-71 mg kg-1) and Pb (6-12 mg kg-1). Also, Cd (6-10 mg
kg -1) and Ag (4 mg kg-1) are high at Easington and Horden. Seaweed at Holy Island
and Bran Sands appears to be the least enriched in trace metals.
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b. Concentrations of Pb, Zn, Cu, Cd, and Ag in F. vesiculosus are usually lower than in
M. edulis from the same area, whereas Mn is normally an order of magnitude higher in
seaweed.
c. The fact that aqua regia-extracted Zn, Cu, and Pb in sediments are positively correlated
with the concentrations of these metals in seaweed, but not to those in mussels,
suggests that metal uptake from ingested sediment is less important than ingestion of
dissolved metal species.
d. Sediments from Roker, Easington, Horden, Blackhall Rocks, and Middleton have
concentrations of Zn, Pb, Ni, Cd, and Ag likely to cause adverse biological effects.
e. The pelitic fraction is usually more enriched in heavy metals, but it represents a very
small portion of the sediment samples (0-6.5% by weight). The fine-grained sand is
also a very important repository of contaminants, especially when mixed with particles
of colliery spoil and secondary mineral and amorphous phases.Coatings of oxides,
hydroxide, or of organic matter can increase significantly the concentration of heavy
metals of particles larger than 63 µm.
In this study, a stronger affinity of most metals for Fe was found in the fine-
grained sand fraction and for Mn in the pelitic fraction. In both fractions, Cr is more
strongly correlated with Mn. The negative correlation between Ag and Fe and between
Ag and Mn reflects the affinity of silver for organic fractions such as humic acids, and
its tendency to form chlorocomplexes in marine water.
f. The heavy metal burden of seaweed (and mussels) at the sites investigated is similar to
those of other polluted areas of the British coastline. Silver enrichment in seaweed is
more pronounced at sites affected by past mining activities, whereas the highest Ag
concentrations in sedi-ments were found at Holy Island and Bran Sands.
g. As sedimentation rates can vary considerably over the year, and dredging is routinely
carried out in the Wear and Tees estuaries, more systematic sam¬pling is necessary to
confirm our preliminary conclusions. One of the limitations of environmental impact
studies based on the analysis of tissue of biomonitors is the fact that a significant
proportion of the dissolved metals present in surface water may be present as
nonbioavailable organic complexes, especially in estuarine areas and near industrial
and sewage outfalls.
If complexation with strong organic ligands takes place, the metal burden found
in seaweed may not be proportional to the dissolved fraction of metals in seawater.
Other information such as salinity, pH, concentration of humic and fulvic acids, and
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concentrationof synthetic chelating agents is required to be able to interpret more

precisely any data of metal uptake from solution by aquatic organisms.

5. Reference
Giusti, L. (2001). Heavy metal contamination of brown seaweed and sediments from
the UK coastline between the Wear river and the Tees river, 26.
http://www.alamy.com/stock-photo/fucus-vesiculosus.html
https://alexhyde.photoshelter.com/image/I0000KwjNctYCfmE
http://www.marlin.ac.uk/species/detail/1421
http://www.marinelifephotography.com/marine/mollusks/bivalves/mytilus-edulis-
complex.htm
http://www.centralcoastbiodiversity.org/pacific-blue-mussel-bull-mytilus-
trossulus.html