Running head: ARSENIC, LEAD, MANGANESE, AND NICKEL IN POSSESSION SOUND 1 Distribution of Arsenic, Lead, Manganese and Nickel in Possession Sound with Relation to Snohomish River Discharge Laura Glastra Ocean Research College Academy, EvCC Spring 2015
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Running head: ARSENIC, LEAD, MANGANESE, AND NICKEL IN POSSESSION SOUND 1
Distribution of Arsenic, Lead, Manganese and Nickel in Possession Sound with Relation to
Snohomish River Discharge
Laura Glastra
Ocean Research College Academy,
EvCC
Spring 2015
ARSENIC, LEAD, MANGANESE, AND NICKEL IN POSSESSION SOUND 2
Abstract
The Snohomish River estuary system is influenced by fresh water sources as well as
exchange with coastal waters. There are many anthropogenic and natural activities in the estuary
that may lead to input of heavy metals such as arsenic, lead, manganese, and zinc. Depending on
the concentration, heavy metals may pose health risks to marine organisms as well as humans
exposed to the metals. Samples of sediments from two locations in Possession Sound were
expected to show variation due to different sediment characteristics, depth, and proximity from
the Snohomish River. It was hypothesized that with increasing seasonal river discharge, there
would be corresponding increases of heavy metal concentration. Statistical analysis comparing
metal concentration and river discharge did not show a strong linear correlation. This suggests
that other internal processes are occurring within the estuary. Continued monthly sampling
cruises, and future research comparing other chemical processes should provide insight on
influences of metal mobility.
ARSENIC, LEAD, MANGANESE, AND NICKEL IN POSSESSION SOUND 3
Distribution of Arsenic, Lead, Manganese and Nickel in Possession Sound with Relation to
Snohomish River Discharge
Heavy metals exist in both particulate and dissolved phases in estuarine systems
(Fukunaga & Anderson, 2011). Fluvial and riverine environments such as estuaries lead to the
dispersal of trace elements such as heavy metals, which makes it increasingly difficult to track
the sources of the metals (Bird, 2011). Tracing the source of contamination is further
complicated in urban environments due to the fact that heavy metals are continuously
accumulating because of anthropogenic activities (Luo, 2015). Various degrees of absorption
efficiency lead to bioaccumulation of heavy metals in organisms that inhabit aquatic
environments (Fukunaga & Anderson, 2011). Furthermore, pollution of heavy metals can
influence vegetative assemblage structure as well as plant productivity. Soils play a crucial role
in supporting estuarine systems, and affect the degree to which plants and animals may be
contaminated. More specifically, soils are involved in biochemical transformations, the cycling
of elements, filtration of water, and supporting plants and infrastructure of the ecosystem (Luo,
2012). The purpose of this study is to outline any spatial trends that may exist in heavy metal
concentration within the Puget Sound estuarine system. Data will be analyzed at two sites that lie
in a smaller body of water, Possession Sound, which is within the greater Puget Sound (Figures 1
and 2). These heavy metals may affect not only marine organisms and the local estuary, but also
be related to the health of humans and other organisms. It is hypothesized that heavy metal
concentrations will be higher at the Buoy site than at Mukilteo. This is hypothesized because
sediment is shallower at Buoy, which allows for more deposition of heavy metals. It is also
ARSENIC, LEAD, MANGANESE, AND NICKEL IN POSSESSION SOUND 4
predicted that heavy metal concentrations at each location will increase correspondingly with
increases in seasonal river discharge.
Sources of Influence
There are various anthropogenic sources contributing to heavy metal contamination in
estuaries and marine ecosystems. Sources of metals can be traced back to long-term
industrialization and rapid urbanization. Long-term industrialization is defined by mining,
metallurgy, and fossil fuel combustion, while rapid urbanization consists of traffic and municipal
solid waste (Luo, 2015). In British Colombia long-term industrialization of leaded gasoline led to
heavy metal contamination of lead, zinc, copper, and cadmium. The study concluded that the
source of contamination was lead because the chronology of its isotope in sediment samples
correlated with gasoline consumption around the Strait of Georgia Basin (Macdonald,
Macdonald, O’Brien, & Gobeil, 1991). Another long-term industrialization source leading to
heavy metal contamination was activity at the Tacoma Copper Smelter throughout the 19th and
20th century (Kuo, Louchouarn, Herbert, Brandenberger, Wade, & Crecelius, 2011). In Pakistan,
rapid urbanization is thought to have led to wastewater contamination. One of these sources of
heavy metals in estuaries is thought to be wastewater contamination from various anthropogenic
causes as well as natural sources. Some of the natural contributors are from the erosion and
weathering of ore deposits and bedrock materials. The noted anthropogenic sources contributing
to heavy metal accumulation are various industrial processes, waste disposal, agricultural
practices, and mining. Additionally, emissions from vehicular traffic are thought to have led to
the atmospheric deposition and emissions of heavy metals that have been transported with rain
ARSENIC, LEAD, MANGANESE, AND NICKEL IN POSSESSION SOUND 5
and storm water. If this water is used for irrigating crops in the area, it poses a potential threat to
humans unless it has been treated prior to irrigation (Khan, Malik, & Muhammad, 2013).
Sources, Movement, and Affects of Specific Heavy Metals
Arsenic. There are various sources that may contribute to arsenic in the environment.
While arsenic can be used in lead-acid batteries for automobiles and in its organic form as a
pesticide in some animal feeds, these sources do not greatly contribute to anthropogenic levels in
the environment. It is also used as a preservative on pressure-treated wood in the form of copper
chromated arsenate (CCA), but this only contributes to low levels of arsenic exposure. The
smelting and mining of copper and lead ores contribute more heavily to arsenic emissions.
Arsenic can also be released into the atmosphere by coal-fired power plants and incinerators
(Toxicological profile for arsenic, 2007).
Once released into the environment, arsenic cannot be destroyed. It can only change form
by becoming attached to or separated from other particles. Smaller particles that may come from
power plants and combustion processes are capable of remaining suspended in air for longer
durations. These particles may be removed from the air by rain, snow, or falling. Sticking to
other particles in water or sediment then transports them. Many arsenic compounds dissolve in
water. Yet, the majority of them remain located in soil/sediment. This is where the larger
particles of arsenic are generally located. Arsenic in aquatic ecosystems is generally so tightly
bonded with other particles and materials that plants and animals are unable to take it in.
However, various species of fish and shellfish can take in an organic arsenic called arsenobetaine.
The arsenobetaine accumulates in tissues, but has not been found to be harmful (Toxicological
ARSENIC, LEAD, MANGANESE, AND NICKEL IN POSSESSION SOUND 6
profile for arsenic, 2007). But, seafood is listed as the primary contributor of arsenic exposure
through food in the Toxicological Profile for Arsenic.
In an attempt to trace arsenic transport routes in estuarine systems, a research team
collected data from 11 different sites during seven sampling cruises from 1997-2001. Because
the Scheldt estuary is well mixed, only surface samples of water were taken to analyze for
suspended and particulate arsenic particles. The research showed that increases of arsenic
corresponded with increases of river discharge, especially during flood times in the winter. In
summer, as river discharge decreased during dry periods, the arsenic values decreased as well. It
was also found that movement of arsenic particulates correlated with the movement of suspended
particulate matter. Therefore, suspended particulate matter could then be used to trace arsenic for
future studies. Another finding from the research showed that arsenic tended to settle in lower
salinity areas that had greater fluxes of sedimentation (De Gieter, M., Elskens, M., & Baeyens,
W, 2005).
The Handbook of Arsenic Toxicology has stated that arsenic exposure to humans is a
worldwide concern. Exposure to humans can occur through drinking, eating, and inhalation
(Ramasamy & Lee, 2015). Exposure during pregnancy may lead to impaired growth or fetal
death as it crosses the placenta. Arsenic exposure at this stage of development correlates with
lower scores on tests of cognitive function (Liua, McDermottb, Lawsona, & Aelion, 2010). Even
in stages of adulthood, arsenic may affect neurological function and reproductive health
(Ramasamy & Lee, 2015). Inorganic arsenic may lead to skin lesions, skin cancer, and
differences in patterns of the skin if exposed for long periods (Toxicological profile for arsenic,
ARSENIC, LEAD, MANGANESE, AND NICKEL IN POSSESSION SOUND 7
2007). Circulatory and peripheral nervous disorders may also develop if exposed at low
concentrations over a long period of time. The Department of Health and Human Services
(DHHS), International Agency for Research of Cancer (IARC), and Environmental Protection
Agency (EPA) have all declared inorganic arsenic to be a human carcinogen. It has been linked
to increased risk of cancer in the liver, bladder and lungs. If inorganic arsenic is swallowed, it
may cause decreased red and white blood cell production, abnormal heart rhythms, and blood
vessel damage. These results may then lead to symptoms such as fatigue, bruising, and nerve
damage. If taken orally at a high enough dose, arsenic poisoning can be lethal (Toxicological
profile for arsenic, 2007).
Lead. The United States (U.S.) previously used tetraethyl and tetramethyl lead to
increase the octane rating of gasoline. Tetraethyl lead is still in use today for off-road vehicles
and airplanes. Presently, the largest use of lead is for storage batteries that are used in vehicles.
Pipes, weights, shot and ammunition, cable covers, and sheets used to shield humans from
radiation have also been known to contain lead. Lead is still mined in the U.S., though primarily
in Alaska and Missouri. Mining and other industries are contributors to the amount of
anthropogenic lead in the environment. Some industries such as lead-acid-battery manufacturing
and brass and bronze foundries release lead into the air. It can also be released into the air by
burning solid waste, coal, or oil containing lead. Furthermore, exhaust from workroom air,
degradation of lead-painted surfaces, fumes and exhaust from lead gas, and volcanoes and
cigarette smoke may release lead into the atmosphere. Lead is removed from the air by rain,
snow, or its particles eventually falling on land and/or surface waters. Another way lead can
enter aquatic systems is through wastewater from iron, steel, and lead producing industries,
ARSENIC, LEAD, MANGANESE, AND NICKEL IN POSSESSION SOUND 8
urban runoff, and piles. This may affect humans if water that has been untreated is being
consumed or used to water crops. Humans can also be exposed to lead if they work at a lead
smelter, refineries, rubber products and plastic industries, soldering, steel welding and cutting
operations, battery manufacturing plants, lead compound manufacturing industries, or if they are
a construction and/or demolition worker (Toxicological profile for lead, 2007).
Metallic lead can only change its state or form because it is resistant to corrosion. If water
is acidic, there is the risk that it may result in lead pipes or solder releasing lead into the
environment. This is problematic because lead released into the environment may remain stuck
to particles in water or soil for many years. Lead that sticks to particles in soil will persist and
generally remain on the upper layer of soil (Toxicological profile for lead, 2007). The chemical
forms of lead were studied in the Pearl River Estuary using sequential chemical extraction
methods from samples of sediment cores. These allowed researchers to compare isotopes and
trace whether they were natural or anthropogenic. Researchers on this team compared the metals
of study to five geochemical terms that may have influenced the movement of lead in the estuary.
These terms were: exchangeable, bound to carbonate phase, bound to iron-manganese oxides,
bound to organic matter, and residual metal phase. In the estuary, the chemical form of the metal
easily influences lead mobility and solubility. It was found that lead increased toward the upper
regions of sediment, which were associated with iron-manganese oxides, residuals, and organic
fractions of the cores. These recent fractions suggest that the abundance of lead in the estuary is
due to rapid urbanization and industrialization (Li, X., Shen, Z., Wai, W.H., & Li, Y-S., 2001).
ARSENIC, LEAD, MANGANESE, AND NICKEL IN POSSESSION SOUND 9
Most lead that plants and animals ingest through the air, water, and soil, will pass through
their systems (Toxicological profile for lead, 2007).
Lead can accumulate in fetal tissues beginning at 12 weeks of pregnancy. While the
general adult population is thought to absorb only 1-20 percent of ingested lead, pregnant women
are believed to absorb up to 70 percent of ingested lead (Toxicological profile for lead, 2007;
Liua et al., 2010). Exposure to a fetus leads to the risks of miscarriage, premature birth, and
lower average birth weights (Toxicological profile for lead, 2007). Young children are still more
vulnerable to lead absorption than adults with approximately 32 percent leaving their bodies as
waste (Toxicological profile for lead, 2007). It is thought that low-level lead exposure at a young
age may lead to neuro-developmental problems such as mental retardation and developmental
delays (Liua et al., 2010; Toxicological profile for lead, 2007). It may also affect a child’s
physical growth. Slower mental development due to exposure in the womb, infancy, or early
childhood correlates with lower intelligence later on in childhood. Furthermore, research
suggests that these effects persist beyond the stages of childhood. If swallowed at slightly higher
amounts, children may experience effects on their blood, development, and behavior. Finally, if
swallowed in large amounts, children may experience anemia, kidney damage, colic (severe
stomach pain), muscle weakness, and brain damage. These results may ultimately lead to cause
of death (Toxicological profile for lead, 2007).
It has been shown that lead exposure primarily targets the nervous system in both
children and adults. In adults, high levels of exposure may lead to severe and potentially lethal
damage of the brain and/or kidneys. High-level exposure in men specifically may damage organs
ARSENIC, LEAD, MANGANESE, AND NICKEL IN POSSESSION SOUND 10
related to the production of sperm. It may also contribute to weakness of the fingers, wrists, or
ankles. Smaller exposure is linked to increases in blood pressure and anemia. There is, however,
no conclusive proof that exposure to lead is carcinogenic to humans (Toxicological profile for
lead, 2007).
Manganese. Manganese is released into the environment during manufacturing processes,
through the use and disposal of manganese based products, due to the actions of industries, and
mining. It can also be released into the air through automobile exhaust since some gasoline
contains manganese additives. Some gases that easily degrade may release manganese into the
environment when exposed to sunlight. Humans may also be exposed to manganese if they are
working or welding in a factory where steel is produced. However, the primary source of
exposure is through foods such as grains, beans and nuts, and to heavy tea drinkers. Once
manganese is released into the environment it cannot be broken down. It can only change form,
or become attached to or separated from other particles. Once in water, it tends to attach itself to
water particles or settle in sediment. The type of soil and chemical state of manganese then
determines the movement of manganese in soil (Manganese, 2008).
From January to December in 1999, researchers sampled for manganese and barium in
the Tillamook Bay Estuary in the Pacific North West. Sampling methods were conducted using a
Niskin bottle deployed to a depth of one meter for dissolved elemental samples. These were later
used to calculate suspended particulate matter, which may influence movement of the manganese
particulates. Surface sediments were collected using a surface sediment grab sampler. Samples
were later frozen and homogenized prior to testing for metal concentration. To analyze input and
ARSENIC, LEAD, MANGANESE, AND NICKEL IN POSSESSION SOUND 11
exchange from rivers and coastal waters, a box model was utilized as a visual representation. The
research showed that as the metal concentrations varied seasonally, they correlated with
suspended particulate materials. It was concluded that adsorption and desorption reactions of
suspended particulates determined seasonal variance of the manganese. Seasonal variance of
manganese was also influenced by benthic sources. Furthermore, the dissolved manganese
values correlated with river discharge rates during winter. This was not true for the other seasons.
It was hypothesized that the lack of correlation could be attributed to internal estuarine processes
such as transport across a sediment-water interface (Colbert, D. & McManus, J., 2005).
Manganese may enter the body through inhalation and ingestion. Miniscule amounts may
enter the body through dermal contact. Of the manganese that enters the body, most will leave
through feces within several days. If a large amount is inhaled, it can lead to lung irritation and
potentially cause pneumonia. Humans may be exposed to manganese if they ingest fish or
shellfish. It has been reported in the journal of Food and Chemical Toxicology that chronic
exposure to manganese through these foods can lead to psychological and neurologic effects that
Figure 19: Pearson Coefficient showing strength of linear correlation between nickel concentration and river discharge at Mukilteo.
ARSENIC, LEAD, MANGANESE, AND NICKEL IN POSSESSION SOUND 33
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