Sarah Henkel Scott Heppell Selina Heppell Kristin and Vince … · 2014-05-20 · D. Ross Robertson Tin: • Most comes from mining, coal & oil combustion, and production & use of

Sarah Henkel Scott Heppell Selina Heppell

Kristin and Vince Politano Scarlett Arbuckle

Dave Cowles

D. Ross Robertson

Mark A. Wilson

Terrance J. Fidler

Project History

•  George Pacific (G-P) discharges treated wastewater through an ocean outfall ~4,000 ft offshore Nye Beach

•  In 2010, water & sediment chemistry and benthic infauna population surveys were conducted by CH2M Hill

o  Water quality samples showed minute traces of 11 metals all well below DEQ levels of concern. Cyanide in water from right at the mouth of the effluent pipe showed concentrations reaching 1/3 a level of concern.

o  In sediment, levels of phenolics and 11 metals were well below US ACE screening criteria and DEQ level of concern.

o  The benthic infauna community within the outfall mixing zone did not differ from communities outside the mixing zone or at reference sites.

Project Overview

•  Goals of this 2012-2013 study: o  Determine if there is bioaccumulation

of effluent-borne pollutants (phenolic compounds, PCBs, or metals) in animals collected from the mixing zone relative to those from reference areas

o  If bioaccumulation is observed, provide a plan for assessing the risk to the ecosystem and public health

o  Provide data to the City of Newport

•  Bioaccumulation = the accumulation of chemicals in the tissues of organisms through any route, including respiration, ingestion, or direct contact with contaminated water, sediment, or pore water in the sediment (US EPA 2000)

Study Organisms

Mussels and Olive snails collected from beaches

Dave Cowles D. Ross Robertson

Mark A. Wilson

Terrance J. Fidler

Dungeness crab, Crangon shrimp, speckled sanddab and rock scallops collected subtidally

Mary Jo Adams

Study Area

•  North Yaquina Reference Area

•  G-P Outfall Primary Survey Area o  Mixing zone o  NMZ, SMZ

•  South Beach Reference Area

•  Seal Rock

•  Moolack Beach (reference area)

•  Nye Beach o  “Nye Beach” o  NBN, NBS

•  Lost Creek/Seal Rock (reference areas)

Offshore Onshore

Sc

Dungeness Crab Collection

Site Date # Crabs

N. Yaquina Reference

8/2/12 20

8/8/12 30

North Mixing Zone

8/2/12 25

8/18/12 19

8/19/12 6

Mixing Zone

8/2/12 32

8/18/12 17

8/19/12 1

South Mixing Zone

8/2/12 36

8/8/12 14

South Beach Reference

8/2/12 10

8/18/12 25

8/19/12 15

3 pots per site, 8 h baited soak

Site Date # Fish mL Shrimp

North Yaquina Reference 9/19/12 5 250

North Mixing Zone 9/19/12 10 250

Mixing Zone 9/19/12 10 250

South Mixing Zone 9/19/12 8 250

South Beach Reference 9/19/12 5 250

Speckled sanddab & Crangon shrimp Collection

5 m otter trawl with 20 mm wall net and 3 mm liner, towed for 5 minutes

Rock Scallop Collection

Site Date #

North Mixing Zone 9/19/13 40

Seal Rock Reference 12/19/13 53

Mussel and Snail Collection

Site Mussels Snails

Moolack Beach 10/17/12 (50) 8/27/12 (50)

Nye Beach North 8/27/12 (50)

Nye Beach 10/17/12 (50) 8/27/12 (50)

Nye Beach South 8/27/12 (50)

Lost Creek 8/28/12 (50)

Seal Rock 10/17/12 (50)

Moolack Beach Lost Creek Beach

Seal Rock Beach

Organic Compounds (GCMS) Trace Metals (ICPMS)

Trace Mercury (CVAFS)

•  What are they?

o  Family of man-made organic chemicals known as chlorinated hydrocarbons

o  Used in hundreds of industrial and commercial applications including electrical, heat transfer, and hydraulic equipment; as plasticizers in paints, plastics, and rubber products; in pigments, dyes, and carbonless copy paper

o  Banned in 1979

•  Why do we worry about them? o  Once in the environment, PCBs do not readily break down and therefore

may remain for long periods of time cycling between air, water, and soil

o  Can accumulate in leaves and above-ground parts of plants and food crops; can be taken up into the bodies of small organisms and fish

o  Demonstrated to cause cancer, as well as a variety of other adverse health effects on the immune system, reproductive system, nervous system, and endocrine system

•  What are they? o  Organobromine compounds that are used as flame retardant

o  Used in building materials, electronics, furnishings, motor vehicles, airplanes, plastics, polyurethane foams, and textiles

o  Structurally akin to the PCBs

o  Industrial production of some PBDEs is restricted under the Stockholm Convention, a treaty to control and phase out major persistent organic pollutants

•  Why do we worry about them?

o  Have been shown to reduce fertility in humans at levels found in households

o  Exposure impairs development of the nervous system & brain and results in thyroid hormone disruption

•  What are they?

o  Class of chemical compounds consisting of a hydroxyl group (—OH) bonded directly to an aromatic hydrocarbon group

o  Components of dyes, polymers, drugs and other organic substances

o  Also related to production and degradation of numerous pesticides and the generation of industrial and municipal sewages

o  Also produced naturally by plants and microorganisms

•  Why do we worry about them? o  Unspecified toxicity and related to the generation of organic radicals and

reactive oxygen species.

o  Can provoke mutagenesis and carcinogenesis in humans and other living organisms

Screened Analytes Detection Limits

Group Extraction/Digestion Analysis MDL

PCB Congeners (n = 52)

Soxhlet extraction with

methylene chloride

Gas Chromatography/Mass Spectrometry

(GCMS)

1 ng/g

Phenols (n = 7) 50 ng/g

Phenols (n = 10) 100 ng/g

Organochlorine Pesticides (n = 18) 1 ng/g

PBDE Congeners by NCI (n = 15) 1 ng/g

Trace metals (n = 22) Milestone microwave digestion

system with nitric/

hydrochloric acid digestion

Inductively Coupled Plasma Mass

Spectrometry (ICPMS)

0.025 µg/g

Trace metals (n = 2) 1 µg/g

Trace Mercury Cold Vapor Atomic Fluorescence

Spectrometry (CVAFS)

0.00001 µg/g

•  Quantitative measure of the toxicity of a chemical to the animal

•  Represent levels of exposure that are associated with low risk for a group of organisms

•  Based on studies of laboratory animals (often a surrogate species) exposed to varying levels of chemical for varying durations of exposure

•  Tissue-based (expressed in units of mg/kg tissue in the exposed animal)

•  “Conservative TRV” for this study is usually a NOED (no observable effects dose) for whole body concentrations

•  “Less Conservative TRV” for this study may be for a particular body part, a LOED, or an LD50

•  Compiled from the Jarvinen and Ankley toxicity/residue database & the U.S. Army Corps of Engineers/U.S. Environmental Protection Agency Environmental Residue-Effects Database (ERED)

Screening Process

•  Mytilus mussels: None Detected

•  Olive snails: None Detected

•  Crangon Shrimp: None Detected

•  Specked Sanddab: None Detected

•  Rock Scallops: None Detected

•  Dungeness Crab: None Detected

• Mytilus mussels: None Detected

• Olive snails: None Detected

•  Crangon Shrimp: None Detected

•  Specked Sanddab: None Detected

• Rock Scallops: None Detected

• Dungeness Crab: 9 PCB congeners & 7

pesticide derivatives detected

• Dungeness Crab: 9 PCB congeners & 7 pesticide derivatives o  7 PCB congeners detected in one SMZ sample (10,000

times < TRV) o  2 PCB congeners detected in one NYR sample (10,000

times < TRV) o  4 pesticide derivatives detected in one MZ sample o  1 pesticide derivative detected in one NMZ sample o  1 pesticide derivative detected in one SBR & one MZ

sample o  1 pesticide derivative detected in 20 samples (4,4’-DDE)

(30 – 300 times < TRV for crabs; 200 – 2000 times < than FDA regulatory limit for human consumption)

Summary of Organics: •  Few detected •  Levels far below any

effects on organisms •  No pattern attributable

to G-P outfall

•  21 detected

•  10 exceeded conservative TRVs for

surrogate species

•  None approached levels of human health

concern

•  None showed patterns of distribution

related to the G-P outfall site

•  19

•  7 (6): Al, As, Cd, Cu, Se, V, Zn (Ba, Mo, Ag, Sr, Sn, Ti,)

•  Yes: Vanadium •  MZ > NYR but SBR

highest

Terrance J. Fidler

Screening Results

•  How many metals detected? •  How many exceeded TRV (or had

no TRV for comparison)? •  Were there differences among sites? •  Were MZ samples higher?

•  19

•  7 (6): Al, As, Cd, Cu, Se, V, Zn (Ba, Mo, Ag, Sr, Sn, Ti,)

•  Yes: Vanadium •  MZ > NYR but SBR

highest

Terrance J. Fidler

Screening Results



Vanadium: •  Mainly enters the environment from natural sources and from the burning of fuel oils •  Does not dissolve well in water but binds strongly to soil and sediments •  Not readily absorbed by the body from the stomach, gut, or contact with the skin (less

than 3 % of ingested vanadium is absorbed into the bloodstream •  Nausea, mild diarrhea, and stomach cramps have been reported in people taking forms

of vanadium for the experimental treatment of diabetes. •  Stomach cramps were reported in a study of people taking 13 mg vanadium/day. •  There is no FDA Regulatory Level for vanadium

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NYR NMZ MZ SMZ SBR

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Vanadium - Dungeness Crab

Conservative TRV (0.6 ug/wet g)

Shore crab (NOED, whole body mortality)

NYR: North Yaquina Reference NMZ: North Mixing Zone MZ: Mixing Zone SMZ: South Mixing Zone SBR: South Beach Reference

•  19 •  5 (3): As, Ba, Fe, Mn, Se

(Sr, Sn, Ti) •  Yes: Fe, Se, Sr, Sn •  Tin: MZ > SBR, highest at

NYR

Screening Results D. Ross Robertson



•  19 •  5 (3): As, Ba, Fe, Mn, Se

(Sr, Sn, Ti) •  Yes: Fe, Se, Sr, Sn •  Tin: MZ > SBR, highest at

NYR

Screening Results D. Ross Robertson

Tin: •  Most comes from mining, coal & oil combustion, and production & use of tin compounds •  Inorganic tin binds to soil and to sediments in water. Some inorganic tin compounds

dissolve in water. Organic tin compounds stick to soil sediment, and particles in water. Organic tin compounds can build up in fish, other organisms, and plants.

•  Breathing, swallowing or skin contact with some organotins, such as trimethyltin and triethyltin compounds, can interfere with the way the brain and nervous system work.

•  The Food and Drug Administration (FDA) regulates the use of some organic tin compounds in coatings and plastic food packaging but has not set consumption limits



-0.6

-0.4

-0.2

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1.6

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Tin - Speckled Sanddab


•  20 •  3 (4): Al, V, Zn (Ba, Sr,

Sn, Ti) •  Yes: Al, Ti, V, Zn

•  Vanadium, Zinc: MZ > NYR but SBR highest

Screening Results

Dave Cowles



•  20 •  3 (4): Al, V, Zn (Ba, Sr,

Sn, Ti) •  Yes: Al, Ti, V, Zn

•  Vanadium, Zinc: MZ > NYR but SBR highest

Screening Results

Dave Cowles

Zinc: •  Most comes from mining, steel production, coal burning, and burning of waste •  Does not dissolve well in water but binds strongly to soil and sediments •  Harmful effects begin at levels 10-15 times higher than the amount needed for good health •  Large doses taken by mouth even for a short time can cause stomach cramps, nausea, and

vomiting. Taken longer, it can cause anemia and decrease the levels of good cholesterol. •  U.S. human health regulations only include limits for exposure in drinking water and

workplace air



Vanadium: •  Mainly enters the environment from natural sources and from the burning of fuel oils •  Does not dissolve well in water but binds strongly to soil and sediments •  Not readily absorbed by the body from the stomach, gut, or contact with the skin (less than

3 % of ingested vanadium is absorbed into the bloodstream •  Nausea, mild diarrhea, and stomach cramps have been reported in people taking forms of

vanadium for the experimental treatment of diabetes. •  Stomach cramps were reported in a study of people taking 13 mg vanadium/day. •  There is no FDA Regulatory Level for vanadium

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Vanadium - Crangon Shrimp


Non-Conservative TRV (3.40 ug/wet g)

Hippolytid shrimp (NOED, whole body morality)

Hippolytid shrimp (NOED, digestive tract, mortality)


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Zinc - Crangon Shrimp



Crayfish (NOED, whole body, mortality)

Crayfish (NOED, muscle tissue, mortality)


•  19 •  2 (7): Al, Ca (Ba, Co, Mo,

Ni, Sr, Sn, Ti) •  Yes: Al, Ba, Co, Mo, Ni, •  Aluminum, Barium

Screening Results



Mary Jo Adams

•  19 •  2 (7): Al, Ca (Ba, Co, Mo,

Ni, Sr, Sn, Ti) •  Yes: Al, Ba, Co, Mo, Ni, •  Aluminum, Barium

Screening Results


no TRV for comparison)? •  Were there differences among sites? •  Were MZ samples higher? Al: •  Aluminum is ubiquitous in the environment. •  For the general population, exposure to aluminum most likely occurs through the

consumption of processed foods, water, and aluminum-containing medicinals. •  Aluminum is poorly absorbed following either oral or inhalation exposure.

Ba: •  Barium and compounds are used in oil and gas drilling muds, automotive paints,

stabilizers for plastics, case hardening steels, bricks, tiles, lubricating oils, and jet fuel as well as in various types of pesticides

•  The general population is exposed to barium through consumption of drinking water and food, usually at low levels.

Mary Jo Adams

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Aluminum - Rock Scallops

Conservative TRV (31 ug/wet g)

MZ: Mixing Zone SR: Seal Rock (Reference)

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Barium - Rock Scallops MZ: Mixing Zone SR: Seal Rock (Reference)

•  How many metals detected? •  How many exceeded TRV (or had no

TRV for comparison)? •  Were there differences among sites? •  Were Nye Beach samples higher?

•  19 •  4 (5): Al, As, Fe, V (Ba,

Mo, Sr, Sn, Ti)

•  Yes: Al, As, Fe, Mo, Sn, V •  Yes: Arsenic highest

in mussels from Nye Beach

Screening Results

Mark A. Wilson

•  How many metals detected? •  How many exceeded TRV (or had no

TRV for comparison)? •  Were there differences among sites? •  Were Nye Beach samples higher?

•  19 •  4 (5): Al, As, Fe, V (Ba,

Mo, Sr, Sn, Ti)

•  Yes: Al, As, Fe, Mo, Sn, V •  Yes: Arsenic highest

in mussels from Nye Beach

Screening Results

Mark A. Wilson

Arsenic: •  Inorganic arsenic compounds are mainly used to preserve wood. Copper chromated

arsenate (CCA) is used to make "pressure-treated" lumber for industrial applications •  Many common arsenic compounds can dissolve in water. Most of the arsenic in water will

ultimately end up in soil or sediment. •  Fish and shellfish can accumulate arsenic; most of this arsenic is in an organic form called

arsenobetaine that is much less harmful. •  Almost nothing is known regarding health effects of organic arsenic compounds in

humans. The FDA regulatory level for consumption of molluscan shellfish is 86 ppm

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Arsenic - Mytilus

Conservative TRV (3.60 ug/wet g) Mytilus edulis

(NOED, whole body, mortality)

FDA regulatory level (not shown) = 86 ug/g

MB: Moolach Beach (N Ref) NB: Nye Beach (near Mixing Zone) SR: Seal Rock (S Reference)


no TRV for comparison)?

•  Were there differences among sites?

•  Were Nye Beach samples higher?

•  21 •  9(6): Al, As, Cr, Cu, Fe, Pb,

Se, Ag, V (Sb, Ba, Mo, Sr, Sn, Ti)

•  Yes: Al, As, Ba, Cr, Fe, Pb, Se, Ag, Sr, Ti, V

•  Yes: all of the above at Nye Beach higher than both reference sites

Screening Results

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Conservative TRV (250 ug/wet g)

Great Pond Snail

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Arsenic - Snails Conservative TRV (3.60 ug/wet g) St. Lawrence Pondsnail

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Barium - Snails

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Chromium - Snails



Sand crab

Sand crab

MB: Moolach Beach NBN: Nye Beach North NB: Nye Beach NBS: Nye Beach South LCB: Lost Creek Beach

My6lus edulis

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Lead - Snails



Sea urchin

Sea urchin

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Selenium - Snails



Asia6c clam

Asia6c clam 0.0

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Silver - Snails



Abalone

Abalone

MB: Moolach Beach NBN: Nye Beach North NB: Nye Beach NBS: Nye Beach South LCB: Lost Creek Beach

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Strontium - Snails

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Titanium - Snails

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Vanadium - Snails


Sea urchin MB: Moolach Beach NBN: Nye Beach North NB: Nye Beach NBS: Nye Beach South LCB: Lost Creek Beach

Determine if there is bioaccumulation of effluent-borne pollutants in animals collected from the MZ relative to those from reference areas •  phenolics •  PBDEs •  PCBs •  metals

•  NOT DETECTED •  NOT DETECTED •  Detected rarely in crabs, no relation to MZ •  No evidence for bioaccumulation associated

with MZ greater than reference areas for subtidal animals

•  Higher concentrations of some metals were detected in olive snails from central beaches but this cannot be attributed solely to GP

•  No concentrations of analytes approached levels of concern for human consumption

Mark A. Wilson

Caveats: •  Mussel watch data are from 2001 –

2007, collected every other year at two sites (red circles: YBFC & YBOP)

•  Values presented are the average of the data available for those 4 years

•  Comparisons are made to the average of 5 replicates from each of the City of Newport Bioaccumulation study sites (orange crosses on map) within a single sample date in 2012

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Arsenic-Mussels TRV (3.6 ug/wet g) a

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FC: Fogarty Creek MB: Moolach Beach (N Ref) NB: Nye Beach (near MZ) SR: Seal Rock (S Reference)

YB: Yaquina Bay

Bars with the same letters over them are values that are statistically the same

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YB: Yaquina Bay

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Copper-Mussels

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Iron-Mussels TRV (68 ug/wet g)

Bars with the same letters over them are values that are statistically the same. If no letters, all samples are statistically indistinguishable


YB: Yaquina Bay

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Lead-Mussels

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Manganese-Mussels

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YB: Yaquina Bay

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Mercury-Mussels

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Nickel-Mussels

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YB: Yaquina Bay

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Selenium-Mussels

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Silver-Mussels



YB: Yaquina Bay

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Tin-Mussels a

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Zinc-Mussels

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Bars with the same letters over them are values that are statistically the same.


YB: Yaquina Bay

Terrance J. Fidler

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Arsenic - Dungeness Crab


FDA Regulatory Level (76 ug/g)

Freshwater crab


Detected concentrations ~ 100 times less than FDA regulatory limit

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Cadmium - Dungeness Crab




Shore crab

Shore crab


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Cadmium - Dungeness Crab




Shore crab

Shore crab


On average, concentrations were half that of the FDA regulatory

limit. However, concentrations in hepatopancreas are typically 10-20 times higher than in musculature. So, humans consume considerably less Cadmium by eating meat than

whole body.

0

2000

4000

6000

8000

10000

12000

NYR NMZ MZ SMZ SBR

Mea

n C

once

ntr

atio

n (

ug/

wet

g)

Copper - Dungeness Crab


National Academy of Sciences (10,000 ug/day)

Shore crab


-10

0

10

20

30

40

50

60

NYR NMZ MZ SMZ SBR

Mea

n C

once

ntr

atio

n (

ug/

wet

g)

Selenium - Dungeness Crab


Institute of Medicine (55 ug/day)


Water flea

Water flea


Detected concentrations ~ 42 times less than FDA regulatory limit

0

200

400

600

800

1000

1200

NYR NMZ MZ SMZ SBR

Mea

n C

once

ntr

atio

n (

ug/

wet

g)

Zinc - Dungeness Crab


Non-Conservative TRV (120 ug/wet g)

Australian Nation Health Action Level (1000 ug/g)

Lobster

Shore crab


Detected concentrations ~ 30 times less than Australian National Health

Action Level (no USA FDA limit)

Documents

Sarah Henkel Scott Heppell Selina Heppell Kristin and Vince … · 2014-05-20 · D. Ross Robertson Tin: • Most comes from mining, coal & oil combustion, and production & use of