Charleston Harbor Marina Copper Study
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  • 1. Andy Lassiter An Internship with Charleston Waterkeeper
  • 2. Charleston Waterkeeper
    • Non-Profit environmental ‘watchdog’
    • Local chapter of Waterkeeper Alliance
    • “ Measurably improving the quality of Charleston’s waterways”
    • Promoting environmentally friendly boat paints
    • CHMCS project as support for future campaign
  • 3. Project Goals
    • Determine 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
  • 4. Presentation Overview
    • Introduction to Copper
    • Environmental Concerns
    • Project Goals / Summary
    • Methods
    • Results
    • Conclusions
    • Recommendations
  • 5.  
  • 6. About Copper
    • Plentiful, naturally occurring element
    • Red, orange, or brown appearance (tarnish)
    • Essential micronutrient to life
    • Metabolic Function, enzyme systems
    • Widely used across the world
    • Agricultural, biocides
  • 7. Main Sources of Copper
    • Agricultural fertilizers and fungicides
    • Metal smelting
    • Mine runoff
    • Fossil fuel combustion
    • Refuse incineration
    • Brake pads
    • Marine paints
  • 8. Antifouling Paints
    • Cu is a common ingredient in marine paints
    • Boats, docks, buoys, construction
    • Est. ~10% of total copper load in waterways
    • Boatyard activities, sanding etc.
  • 9. Fate & Transport
    • Two phases
    • Dissolved in water column
    • Particulate: dissolved in sediment
    • Particulates transported with sediments
    • Do not break down
    • Bioaccumulation
  • 10. Mode of Action
    • Several modes of action
    • Non-specific binding
    • Inhibits basic osmotic balance
    • Inhibits respiratory electron transport (respiratory failure)
    • Bonds to proteins and DNA
    • Bind to fish gills
    • Inhibits nutrient uptake
  • 11. Cu toxicity comparison
    • Cu toxicity varies widely across species
    • From 1 ug/L for algae and fungi
    • To 346,700 ug/L for crabs
    • Salinity, pH, DOC (dissolved organic carbon)
    • Differences in physiology
    • Size
    • Benthic organisms are highly sensitive
  • 12. Environmental Concerns
    • Cu 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
  • 13. Local Concerns
    • marine habitat, spawning,
    • reproduction, and development
    • wildlife habitat
    • commercial and sport fishing
    • bioaccumulation > humans
    • water contact recreation
    High levels of Cu have an adverse effect on fish and wildlife. And that's why we care!
  • 14.  
  • 15. Goals for CHMCS project
    • Determine 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
  • 16. Overview
    • 60 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
  • 17. Sampling Locations
  • 18. Sampling Locations
    • Spatially distributed
    • Representative of various types of facilities
    • Differences in marinas with boatyards
    • Remote reference site in the Stono River
  • 19. Sampling Categories
    • 60 Total Samples
    • 18 per location + 6 control samples
    • Divided into 3 categories per location
    • Upstream / Downstream / Proximity
    • Remote reference site, away from potential anthropogenic Cu inputs
  • 20. Sampling Categories
  • 21. Sampling Format
    • Comparisons between marinas
    • Upstream / downstream differences
    • Examine transport away from theorized sources
    • If Cu settles into nearby marine sediments, significant differences are likely.
    • If boatyards are source, significant differences are likely.
  • 22. Sample Collection
    • 3 Sampling events, Jan. 19 th , 24 th , 25th
    • Petite ponar grab sampler, scoops
    • Upper 10cm of sediment surface
    • Sterile technique
    • Composites
    • Stored in clear plastic
    • GPS locations
    • Tide / Weather / Depth
  • 23.  
  • 24.  
  • 25.  
  • 26. Sample Testing
    • Wet sediment samples, must be dried
    • Samples sent to QROS-US Laboratories
    • Samples tested via X-Ray Fluorescence (XRF)
  • 27. About XRF
    • Cutting Edge Technology
    • X-MET 5100 – Oxford Instruments
    • Samples bombarded with X-Rays
    • Accurate and reliable identification of heavy element pollutants
    • Laboratory quality analytical data
    • High accuracy
    • Low detection limits
    • Ideal for soil contaminants at low ppm levels
  • 28. Data Analysis
    • First, 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
  • 29. Data Analysis
    • Threshold 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
  • 30.  
  • 31. Charleston Boatyard
    • Wando 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
  • 32. Charleston Boatyard This figure shows the approximate sample locations and Cu concentration in µg / dry g
  • 33. Coded Data for City Boatyard Sample ID CONC. ( µg/g ) NOAA SQuiRT Levels for Cu   CB-01-BP-1 15 <Threshold 0 - 18.6 µg/g CB-02-BP-2 3 TEL 18.7 µg/g CB-03-BP-3 23 ERL 34 µg/g CB-04-LS-1 5 ERM 270 µg/g CB-05-LS-2 6 CB-06-LS-3 45 Average Cu. Conc by Category   CB-07-US-1 28 BP / LS US DS CB-08-US-2 18 15 28 3 CB-09-US-3 4 3 18 3 CB-10-US-4 4 23 4 2 CB-11-US-5 3 5 4 3 CB-12-US-6 9 6 3 3 CB-13-DS-1 3 45 9 3 CB-14-DS-2 3 16.2 11.0 2.8 CB-15-DS-3 2 Exceedences 2 1 0 3 CB-16-DS-4 3 CB-17-DS-5 3 CB-18-DS-6 3
  • 34. Average Concentration by Category
    • Average Cu concentrations were 16.17 for Proximity, 2.83 for Downstream, and 11.0 for Upstream
  • 35. Charleston City Marina
    • Ashley River
    • Moderate levels of Cu overall
    • Six total samples exceeded the TEL.
    • 50 percent of the Proximity samples exceeded the TEL.
  • 36. This figure shows the approximate sample locations and Cu concentration in µg / dry g
  • 37. 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 9.7 CM-15-DS-3 9 3 2 1 CM-16-DS-4 3 CM-17-DS-5 3 CM-18-DS-6 12
  • 38. Average Concentration by Category
    • Average Cu concentration is 23.5 for Proximity, 9.67 for Downstream, and 16.17 for Upstream.
  • 39. Dolphin Cove Marina
    • Ashley 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
  • 40. This figure shows the approximate sample locations and Cu concentration in µg / dry g.
  • 41. 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
  • 42. Average concentration by Category
    • Average concentrations were 97.3 for Proximity, 70.7 for Downstream, and 120.5 for Upstream.
  • 43. Control Location
    • Located 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
  • 44. Control Location NOAA Cu SQuiRT Levels   <Threshold 0 - 18.6 µg/g TEL 18.7 µg/g ERL 34 µg/g ERM 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
  • 45. Comparisons by Location Shows average BP Concentrations for each site.
  • 46.  
  • 47. Statistical Analysis
    • Determine 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
  • 48. Statistical Analysis
    • Full 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 Table Response: 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
  • 49. Conclusions
    • All 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
  • 50. Future Studies
    • Relatively small scale project
    • Better spatial layout
    • Greater number of samples
    • Sediment toxicity testing
  • 51. Reality
    • Copper is here to stay
    • Production is still rising, use increasing
    • Maintain environment through monitoring
    • Sediment testing, toxicity testing, regulations
    • Minimize negative impact, prevent spikes
    • Pursue new technology
  • 52. Innovative Tech.
    • Bioswales in WA
    • Wastewater seeps through
    • grass, soil, and gravel, then
    • Filtered again.
    • Reduced concentrations from 4,700 ppb, to 91ppb
    • $400,000
    • Eco-friendly paints
    • Regulation
  • 53. 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.
  • 54. Special thanks to Charleston Waterkeeper, committee members, and friends who helped with the CHMCS project!