Andy Lassiter

An Internship with Charleston Waterkeeper

Charleston WaterkeeperNon-Profit environmental ‘watchdog’Local chapter of Waterkeeper Alliance“Measurably improving the quality of

Charleston’s waterways”Promoting environmentally friendly boat

paintsCHMCS project as support for future

campaign

Project GoalsDetermine if copper (Cu) based marine

antifouling paints are a significant source of Cu contamination to the sediments near marinas and boatyards, and Charleston Harbor in general

Provide useful scientific data and support to Charleston Waterkeeper to help facilitate the development of their upcoming copper campaign

Presentation OverviewIntroduction to CopperEnvironmental ConcernsProject Goals / SummaryMethodsResultsConclusionsRecommendations

About CopperPlentiful, naturally occurring elementRed, orange, or brown appearance (tarnish)Essential micronutrient to lifeMetabolic Function, enzyme systemsWidely used across the world Agricultural, biocides

Main Sources of CopperAgricultural fertilizers and fungicidesMetal smeltingMine runoffFossil fuel combustionRefuse incinerationBrake padsMarine paints

Antifouling PaintsCu is a common ingredient in marine paintsBoats, docks, buoys, constructionEst. ~10% of total copper load in waterwaysBoatyard activities, sanding etc.

Fate & TransportTwo phasesDissolved in water columnParticulate: dissolved in sedimentParticulates transported with sedimentsDo not break downBioaccumulation

Mode of ActionSeveral modes of actionNon-specific bindingInhibits basic osmotic balanceInhibits respiratory electron transport

(respiratory failure)Bonds to proteins and DNABind to fish gillsInhibits nutrient uptake

Cu toxicity comparisonCu toxicity varies widely across speciesFrom 1 ug/L for algae and fungi To 346,700 ug/L for crabsSalinity, pH, DOC (dissolved organic carbon)Differences in physiologySizeBenthic organisms are highly sensitive

Environmental ConcernsCu does not break down, and will

bioaccumulate

Causes toxicity as low as 1ug/L

Very common at marinas and boatyards

Case study: Pacific Coho salmon

New Regs- discharge limits as low as 14ppb

Local Concernsmarine habitat, spawning, reproduction, and development wildlife habitatcommercial and sport fishingbioaccumulation > humans water contact recreation

High levels of Cu have an adverse effect on fish and wildlife. And that's why we care!

Goals for CHMCS projectDetermine if copper (Cu) based marine

antifouling paints are a significant source of Cu contamination to the sediments near marinas and boatyards

Test whether Cu concentrations are higher in close proximity to these potential anthropogenic inputs from marinas and boatyards

Overview60 sediment samples were collected from 3

representative marinas/boatyards, control site

Upstream / Downstream / Proximity

Scanned for metal concentration

Compared to NOAA threshold levels for marine sediment

Statistical data analysis

Sampling Locations

Sampling Locations

Spatially distributed

Representative of various types of facilities

Differences in marinas with boatyards

Remote reference site in the Stono River

Sampling Categories60 Total Samples18 per location + 6 control samplesDivided into 3 categories per locationUpstream / Downstream / ProximityRemote reference site, away from potential

anthropogenic Cu inputs

Sampling Categories

Sampling FormatComparisons between marinasUpstream / downstream differencesExamine transport away from theorized

sources

If Cu settles into nearby marine sediments, significant differences are likely.

If boatyards are source, significant differences are likely.

Sample Collection3 Sampling events, Jan. 19th, 24th, 25thPetite ponar grab sampler, scoopsUpper 10cm of sediment surfaceSterile techniqueCompositesStored in clear plasticGPS locations Tide / Weather / Depth

Sample TestingWet sediment samples, must be driedSamples sent to QROS-US LaboratoriesSamples tested via X-Ray Fluorescence (XRF)

About XRFCutting Edge TechnologyX-MET5100 – Oxford InstrumentsSamples bombarded with X-RaysAccurate and reliable identification of heavy

element pollutantsLaboratory quality analytical dataHigh accuracyLow detection limitsIdeal for soil contaminants at low ppm levels

Data AnalysisFirst, a determination of whether each site exceeded

NOAA Screening Quick Reference Tables (SQuiRTS)

Consider various published toxicological benchmark screening values for marine sediments

Based upon empirical relationships between sediment concentrations and observed toxicity bioassay results or observed benthic community impacts

Used to identify potential impacts to coastal resources and habitats potentially affected by hazardous waste sites

Statistical Analysis

Data AnalysisThreshold Effects Level – TEL - chemical

concentration that when ingested by an organism, above which some effect (or response) will be produced and below which it will not

Effects Range Low – ERL - concentration of a contaminant above which harmful or adverse effects may be expected to occur

Effects Range Median – ERM - concentration of a contaminant above which harmful effects always or almost always occur.

NOAA SQuiRT Levels for Cu

TEL 18.7 µg/ dry g

ERL 34 µg/ dry g

ERM 270 µg/ dry g

Charleston BoatyardWando River

Lowest levels overall

Moderate to low levels of Cu contamination

Three samples exceeded the TEL

Average concentration higher in close proximity

By visual inspection, most obvious pattern

Charleston Boatyard

This figure shows the approximate sample locations and Cu concentration in µg / dry g

Coded Data for City BoatyardSample ID CONC. (µg/g) NOAA SQuiRT Levels for Cu CB-01-BP-1 15 <Threshold 0 - 18.6 µg/gCB-02-BP-2 3 TEL 18.7 µg/gCB-03-BP-3 23 ERL 34 µg/gCB-04-LS-1 5 ERM 270 µg/gCB-05-LS-2 6CB-06-LS-3 45 Average Cu. Conc by Category CB-07-US-1 28 BP / LS US DSCB-08-US-2 18 15 28 3CB-09-US-3 4 3 18 3CB-10-US-4 4 23 4 2CB-11-US-5 3 5 4 3CB-12-US-6 9 6 3 3CB-13-DS-1 3 45 9 3

CB-14-DS-2 3 16.2 11.0 2.8CB-15-DS-3 2 Exceedences 2 1 0 3CB-16-DS-4 3CB-17-DS-5 3CB-18-DS-6 3

Average Concentration by CategoryAverage Cu concentrations were 16.17 for

Proximity, 2.83 for Downstream, and 11.0 for Upstream

Charleston City MarinaAshley River

Moderate levels of Cu overall

Six total samples exceeded the TEL.

50 percent of the Proximity samples exceeded the TEL.

This figure shows the approximate sample locations and Cu concentration in µg / dry g

Sample ID CONC. (µg/g) NOAA SQuiRT Levels for Cu

CM-01-BP-1 28 <Threshold 0 - 18.6 µg/g

CM-02-BP-2 67 TEL 18.7 µg/g

CM-03-BP-3 17 ERL 34 µg/g

CM-04-LS-1 19 ERM 270 µg/g

CM-05-LS-2 7

CM-06-LS-3 3 Average Cu. by Category

CM-07-US-1 29 BP / LS US DS

CM-08-US-2 12 28 29 11

CM-09-US-3 12 67 12 20

CM-10-US-4 14 17 12 9

CM-11-US-5 27 19 14 3

CM-12-US-6 3 7 27 3

CM-13-DS-1 11 3 3 12

CM-14-DS-2 20 23.5 16.2 9.7CM-15-DS-3 9 3 2 1

CM-16-DS-4 3

CM-17-DS-5 3

CM-18-DS-6 12

Average Concentration by CategoryAverage Cu concentration is 23.5 for

Proximity, 9.67 for Downstream, and 16.17 for Upstream.

Dolphin Cove MarinaAshley River

Moderate to extremely high Cu levels overall

13 / 18 Samples exceeded the TEL

100% of Proximity samples exceeded TEL

Extremely high levels in some samples

Could be indicative of historical or industrial contamination

This figure shows the approximate sample locations and Cu concentration in µg / dry g.

Sample ID CONC. (µg/g) NOAA SQuiRT Levels for Cu

DC-01-BP-1 19 <Threshold 0 - 18.6 µg/g

DC-02-BP-2 395 TEL 18.7 µg/g

DC-03-BP-3 31 ERL 34 µg/g

DC-04-LS-1 23 ERM 270 µg/g

DC-05-LS-2 51

DC-06-LS-3 65

DC-07-US-1 15 Average Cu. by Category

DC-08-US-2 45 BP / LS US DS

DC-09-US-3 93 19 15 100

DC-10-US-4 346 395 45 254

DC-11-US-5 218 31 93 9

DC-12-US-6 6 23 346 42

DC-13-DS-1 100 51 218 15

DC-14-DS-2 254 65 6 4

DC-15-DS-3 9 97.3 120.5 70.7

DC-16-DS-4 42 6 4 3

DC-17-DS-5 15

DC-18-DS-6 4

Average concentration by CategoryAverage concentrations were 97.3 for

Proximity, 70.7 for Downstream, and 120.5 for Upstream.

Control LocationLocated near the confluence of the Kiawah and

Stono Rivers

Away from potential anthropogenic Cu inputs

Very low levels overall

Barely detectable levels at all sampling locations

No threshold exceedences

Control Location

NOAA Cu SQuiRT Levels <Threshold 0 - 18.6 µg/gTEL 18.7 µg/gERL 34 µg/gERM 270 µg/g

# Conc. (ppm) GPS LAT. GPS LONG. TIME Depth (ft.) TIDE

C1 3 32 62.915 80 01.334 5:15 7.00 out

C2 2 32 62.667 80 00.899 5:15 2.00 out

C3 3 32 62.492 80 01.412 5:15 4.00 out

C4 3 32 67.389 80 00.662 5:30 6.40 out

C5 3 32 67.192 80 00.664 5:30 3.00 out

C6 3 32 66.533 80 00.857 5:30 6.00 out

Comparisons by Location

Shows average BP Concentrations for each site.

Statistical AnalysisDetermine if Cu concentrations were statistically

significant between locations

One way ANOVA for each marina

Data did not hold up to normality assumptions of normal distribution and equal variance

Log transformations were applied to dataset

Bartlett’s Homogeneity of Variance tests ensured the assumptions would hold up

Statistical AnalysisFull two-way ANOVA was then run on entire dataset

Low P-Value of .045 indicates statistical significance between location and category.

Reject null hypothesis: that Cu concentrations were equal by location.

Data was unlikely to occur by chance. Suggests dataset indicates a legitimate trend, that Cu levels were influenced by proximity to marinas/boatyard

Analysis of Variance TableResponse: log(Cu.Conc.) Df Sum Sq Mean Sq F value Pr(>F) Marina 2 35.882 17.941 15.4532 7.781e-06 ***Location 2 7.719 3.859 3.3242 0.04503 * Marina:Location 4 1.091 0.273 0.2350 0.91720 Residuals 45 52.245 1.161 ---Signif. codes: 0 ‘***’ 0.001 ‘**’ 0.01 ‘*’ 0.05 ‘.’ 0.1 ‘ ’ 1

ConclusionsAll marinas tested exceeded the NOAA TEL for

Cu to some extent.

Overall patterns and analysis suggest that there are significantly higher concentrations of Cu in sediment to marinas / boatyards.

Control location, away from Cu inputs, showed negligible Cu levels

Antifouling boat paints are a known source of Cu and are likely responsible for the contamination

Future StudiesRelatively small scale project

Better spatial layout

Greater number of samples

Sediment toxicity testing

RealityCopper is here to stayProduction is still rising, use increasingMaintain environment through monitoringSediment testing, toxicity testing, regulationsMinimize negative impact, prevent spikesPursue new technology

Innovative Tech.Bioswales in WAWastewater seeps through grass, soil, and gravel, then Filtered again. Reduced concentrations from 4,700 ppb, to

91ppb$400,000Eco-friendly paintsRegulation

What can Waterkeeper do? Public Policy- A non-binding resolution by the City of Charleston to

eliminate the use of toxic bottom paint in Charleston Harbor, and the implementation of specific city policies to motivate boaters to switch to non-toxic bottom paints.

Boater Education- Waterkeeper, the City of Charleston, and local marinas can educate boaters on the problems copper pollution is causing in the harbor, the benefits of non-toxic bottom paints, and the non-toxic bottom paint options available. 

Financial Incentives - provide a small monetary incentive based on a percentage of the cost for the boat owner to switch to non-toxic paint.

Resources & Support- Assist cooperating local boatyards and hull cleaning services in identifying and supporting the use of appropriate non-toxic bottom paints and developing non-toxic paint services.

Water Monitoring- We will conduct water monitoring for dissolved copper in the Charleston Harbor watershed to document improvements in water quality, and analyze the data to determine the copper load reductions achieved in respective marinas and harbor wide.

Special thanks to Charleston Waterkeeper, committee members, and friends who helped with the CHMCS project!