1. Metal Loadings to the Hudson River and New York Harbor: How have they changed? Robert Mason Department of Marine Sciences University of Connecticut, Groton, CT 06340 Mostly based on data collected and analyzed during a project funded by the Hudson River Foundation (Fitzgerald and Mason as PI’s)

2. Outline Why we care about metals in the Hudson? Sediment Data Water Data – Factors controlling distributions in the upper estuary and NY/NJ Harbor Water Data – Changes over time Mass Balances for the Metals - Sources to the Harbor, and major sinks

3. Metal Toxicity? 1) Impact is on lower food chain organisms for most metals as bioaccumulation is greatest for plankton. In the Hudson, Cd is the most important example as there are known point source contamination (e.g. Foundry Cove) that been shown to cause toxicity. However, organisms were able to generate resistance to the Cd. 2) Toxicity of highly bioaccumlative compounds is manifest in the higher level consumers and toxicity to plankton may not occur. Example is methylmercury which has most impact for higher food chain consumers (humans, mammals and birds) that feed on piscivorous fish Levington et al 2008

4. EPA A number of species exceed the EPA recommended value for mercury (assuming all as methylmercury ) Health of the Harbor report

5. Gobeille et al., 2006

6. People consuming local fish have higher mercury levels than those who do not. Levels found in Hudson River similar to that for other ecosystems where people eat local fish Levels below the EPA suggested reference level of 5.8 ng/mL.

7. Sediment Concentrations Levels of metals in sediments of the Hudson River are elevated above other US estuaries and higher than background concentrations Taken from Bopp et al., Ch 24

9. Changes in Sediment Metal Conc (ppm) between 1960’s & 1990’s

10. From Bopp et al., Ch 24

11. Sediment Concentration Changes For most metals and locations, there has been a dramatic decrease in concentration between 1960’s and 1990’s In mainstem, no trend in concentration with distance Changes somewhat less dramatic in the lower estuary Concentrations still elevated above background for many metals. How does this impact the ecosystem?

12. Relative change in fish concentration less than that of sediment for Hg. Also fish do not track sediment concentration Levinton & Pochron, 2008

13. u Data summarized was derived from a variety of literature sources and databases. Evaluated for appropriateness of the analytical methods and complete presentation of quality assurance/quality control (QA/QC) procedures and results. u Large databases included CARP (Contaminant Assessment and Reduction Project), EMAP (Environmental Monitoring and Assessment Project), and data from regulatory agencies (e.g., NYSDEC State Waters Monitoring Section [SWMS] and Division of Water). u Most published studies have reported surface and deep water concentrations of metals (Hg, Cd, Cu, Fe, Ni, Zn, Ag, and Pb) in the lower Hudson (south of Newburg; ~25 to 100 km north of the Battery) and the estuarine turbidity maximum (ETM; south of the Harlem River; ~ 4 to 25 km). Sources of Data Assessment of Water Column Data

14. Kingston-Poughkeepsie Glenmont Cohoes Waterford 0 10 20 30 Km Hudson River Watershed NY/NJ Harbor Hudson River Estuary Metal Atomic Mass 1 ug/L = x nM 1ppm = x nmol/g Ni58.717.0 Cu63.515.7 Zn65.415.3 Cd112.48.9 Hg200.65.0 Pb207.24.8

15. Water - Middle & Upper Hudson (SWMS; collected 1993-2006; mean ± SD)

16. Water - Middle & Upper Hudson (CARP; collected 1999-2001; mean ± SD)

17. TSS - Upper Hudson/Sources of Metals (SWMS; collected 1993-2006; mean ± SE)

18. TSS - Upper Hudson Sources of Hg (CARP & SWMS; collected 1999-2001; mean ± SE)

19. Spatial/seasonal MMHg distributions (CARP; collected 1999-2000; mean ± SE)

20. u Average total (filtered + particulate) concentrations of Hg (58 to 130 pM), Cu, Ni, Zn, and total suspended solids (TSS) in surface waters are highest at Poughkeepsie. u Cd (0.97 to 1.3 nM) and Pb were more uniformly distributed in the middle and upper Hudson. u Fe-normalized suspended particle concentrations of Hg, Cd, Pb, Cu, Ni, and Zn were elevated in the upper Hudson at Waterford and Cohoes as compared to Poughkeepsie, indicating watershed sources of trace metals. u MMHg in the middle and upper Hudson is likely derived/connected to net production in the Hudson River watershed. Summary middle and upper Hudson

21. Hudson River - Water (Lower Hudson and ETM) (CARP; collected 1999-2001; mean ± SE)

22. u In the estuarine turbidity maximum (ETM), average total Cd concentrations (0.74 to 1.2 nM, surface waters) are similar to the middle and upper Hudson sites, while average total Hg (54 to 1110 pM, surface and bottom waters) is elevated as compared to the rest of the upper Hudson. u The filtered fraction of Cd increases dramatically with salinity (83 to 120% of total Cd) in the lower Hudson River, and higher total Hg and Cd levels are associated with spring high flow periods. u Average surface water suspended particle concentrations of Hg (2.20 to 3.54 nmol g -1 ) and Cd (5.45 to 12.6 nmol g -1 ) are largely overlapping between the ETM and lower Hudson. u ETM and upper Hudson suspended particle metals concentrations are elevated as compared to the middle Hudson (Poughkeepsie), indicating sources of metals in both regions. Summary Lower Hudson and ETM

23. Major Rivers – NY/NJ Harbor (CARP; mean ± SE; collected 1999-2001)

24. u Average total Hg (145 and 433 pM, surface and bottom waters) and Cd (0.97 and 1.35 nM) concentrations at the mouth of the Passaic River were elevated as compared to the Hudson ETM, while only total Hg (109 pM) was elevated at the mouth of the Hackensack River. u Concentrations in the lower East River and the Raritan River were similar to levels in the Hudson ETM. u Average suspended particle Hg (9.8 to 20.8 nmol g -1 ) and Cd (9.6 to 49.2 nmol g -1 ) concentrations were elevated in both the Hackensack and Passaic as compared to the Hudson, although suspended particle Cd was less near the mouths of rivers. Summary - Rivers

25. NY/NJ Harbor - Water (CARP; collected 1999-2001; mean ± SD)

26. NY/NJ Harbor Water (Balcom et al. 2008; collected 2002-2003; mean ± SD)

27. NY/NJ Harbor - Water (Paulson, 2005; collected 1999; mean ± SD)

28. Temporal Comparison Water Klinkhammer and Bender (1981) collected 1974-1975 NY Bight Paulson (2005) collected 1999 Rockaway-Sandy Hook transect (mean ± SD) Sañudo-Wilhelmy and Gill (1999) reported a similar decrease in dissolved metals for the Hudson ETM and Lower Harbor between 1974/1975 and 1995/1997.

29. NY/NJ Harbor – Recent Sediment (CARP, collected 1999-2001; EMAP, surface sediment collected 1998; mean ± SD) Circles are data not included in the averages as considered outliers

30. NY/NJ Harbor - Recent Sediment (Balcom et al., 2008 and Hammerschmidt et al., 2008 suspended particles and surface sediment collected 2002-2003; mean ± SD) Circles - data not included in the averages

31. NY/NJ Harbor – Recent Sediment (Paulson, 2005, suspended particles collected 1999; EMAP, surface sediment collected 1998 and 1993-1994; mean ± SD) Circles - data not included in the averages

32. ETM and NY/NJ Harbor - Ratios (Paulson, 2005 and Feng et al., 2002 - suspended particles collected 1994-1999 ; EMAP, surface sediment collected 1998 and 1993-1994; mean ± SE)

33. ETM and NY/NJ Harbor - Ratios (Paulson, 2005 and Feng et al., 2002 - suspended particles collected 1994-1999 ; EMAP, surface sediment collected 1998; mean ± SE)

34. u Regional average trace metal concentrations of Hg (3.2 to 166 pM) and Cd (0.19 to 0.90 nM) in NY/NJ Harbor were generally elevated and more variable near the input of major rivers in Newark Bay and the Upper Harbor, roughly corresponding with elevated TSS levels. u Harbor Hg and Pb were mainly in the particulate phase, while Cd, Cu, and Ni have more metal in the dissolved fraction at elevated Harbor salinities. u Over 25 years (1974 to 1999), average dissolved metals concentrations (surface and deep) in the Lower Harbor and NY Bight region were reduced by 85 to 90%. Summary – NY/NJ Harbor

35. u There was good agreement between average suspended particle concentrations of Hg (1.1 to 8.7 nmol g -1 ), Cd (3.1 to 13.2 nmol g -1 ), and other metals with surface sediment concentrations in the Harbor, while suspended particle concentrations in the ETM are known to be elevated as compared to sediments (Feng et al., 2002). u However, Al- and Fe-normalized suspended particle metal concentrations were reduced in the Hudson ETM and elevated in Raritan Bay and at the Rockaway-Sandy Hook transect suggesting metals enrichment due to association with fine particulate material or particulate organic matter. Summary – NY/NJ Harbor (continued)

36. Budget sources – percent inputs (mean ± SE) Hg - 3100 moles y -1 Cd - 25 K moles y -1 MMHg - 14 moles y -1

37. Budget sources – percent inputs (mean ± SE) Pb - 850 K moles y -1 Cu - 2800 K moles y -1 Ni - 1700 K moles y -1 Zn - 7100 K moles y -1

38. Temporal Comparison of Metal Inputs (mean ± SE or range) Reference Sampling Period Cd (K moles y -1 ) Ni (K moles y -1 ) Cu (K moles y - 1 ) Zn (K moles y -1 ) This Study~ 2000 - 200625 ± 7.41700 ± 5802800 ± 6607100 ± 2100 Klinkhammer & Bender (1981) April 1974280 - 5904500 - 9500 5200 - 10000 11100 - 28300 (enhancement)(11 to 24 x)(2.5 to 5.5 x)(2 to 3.5 x)(1.5 to 4 x) October 1975190 - 5003400 - 75004000 - 84007000 - 15100 (enhancement)(8 to 20 x)(2 to 4.5 x)(1.5 to 3 x)(1 to 2 x) Decrease most dramatic for Cd - >90% reduction in inputs. Other metals show more modest reductions over time.

39. u Current annual loadings (~2000 to 2006) to NY/NJ Harbor estimated for Hg (3100 mol y -1 ), MMHg (37 mol y -1 ), Cd (25 Kmol y -1 ), Pb (850 Kmol y -1 ), Ni (1700 Kmol y -1 ), Cu (2800 Kmol y -1 ), Zn (7100 Kmol y -1 ) u The majority of inputs are from rivers (38 to 88% of totals). u River fluxes of metals were estimated independently using a Hudson sediment delivery flux (8.12 ± 3.25 x 10 11 g y -1 ; Wall et al. [2008] and HydroQual [2003]) and mean suspended particle metals concen- trations in the middle/lower Hudson. These estimates agreed well with the annual loadings shown above. u Total inputs are significantly decreased for Cd (8 to 42x), Ni (2 to 5.5x), Cu (1.5 to 3.5x), and Zn (1 to 4x) since the mid 1970s (25 to 30 years). u The relative contribution of metals from sewage has decreased. u Hg inputs are likely to have declined by about a factor of 3-5 since the mid-1960s. Summary – Mass Balances

40. u There is a need for high quality time series measurements of filtered and suspended particle metals concentrations, as well as important ancillary parameters (e.g., POC), in the waters of the Hudson River and NY/NJ Harbor. u The decline in metals concentrations in the waters of NY/NJ Harbor since the mid-1970s was established by a comparison between adjacent regions. The time series of measurements is incomplete for any one region of the Harbor. u Limited measurements (1999-2001) of Hg and Cd concentrations in the middle and upper Hudson, major regions of the Harbor, and the East River, with almost no data on suspended particle concentrations. Conclusions

41. u The sediment-water fluxes of most trace metals has not been measured in NY/NJ Harbor, and are needed considering the importance of this source term in some mass balances (e.g., MMHg) u Bulk (wet and dry) atmospheric deposition measurements are limited for most metals in the Harbor region, and are important to mass balances since atmospheric deposition of metals and subsequent yield from watersheds accounts for a substantial portion of the fluxes of metals in rivers. u We hypothesize that much of the MMHg in NY/NJ Harbor is likely connected to net production in the Hudson River watershed, and that there is limited MMHg input from river sediments. Conclusions (continued)

43. Seasonal distributions of Hg (CARP; collected 1999-2000; mean ± SE)

44. Mass balances - NY/NJ Harbor Sources Hg (moles y -1 ) MMHg (moles y -1 ) Cd (K moles y -1 ) Rivers2100 ± 82023 ± 914 ± 6.4 East River700 ± 2002.9 ± 0.56.5 ± 0.7 WPCF’s140 ± 153.7 ± 0.42.1 ± 0.3 Atmospheric Deposition60 ± 50.9 ± 0.11.1 ± 0.2 Benthic Flux60 ± 1308 ± 41.1 ± 3.7 Total3100 ± 90037 ± 1025 ± 7.4 (moles y -1 ) (K mol y -1 ) Sinks Estuarine Exchange1300 ± 27014 ± 2.018 ± 2.4 Evasion60 ± 20-- Sediment Burial1700 ± 900 1 4.0 ± 3.06.7 ± 8.0 1 (Photo)demethylation--2.0 ± 1.0-- Biological Processes--17 ± 11 1 -- Total31003725 (mean ± SE; ~2000 to 2006) 1 closing term

45. u Watershed Hg yields were estimated to range from 0.011 to 0.019 µmol m -2 y -1 (25-30% of atmospheric wet deposition) resulting in delivery of 480 to 780 mol Hg y -1 to the major rivers surrounding the Harbor (Balcom et al., 2008). u Watershed fluxes are estimated to account for 23 to 37% of the Hg flux from rivers to NY/NJ Harbor (2100 ± 820 mol y -1 ) u Assuming that the watershed yield of MMHg is 3% of the HgT flux (based on atmospheric deposition measurements), watershed MMHg yields are estimated to range from 3.4 to 5.6 x 10 -4 µmol m -2 y -1 (Driscoll et al. [1998] reported 8.4 x 10 -4 µmol m -2 y -1 ), resulting in delivery of 14 to 23 mol y -1 to rivers. u Indicates that watershed delivery may account for the majority of the MMHg flux from rivers to NY/NJ Harbor (23 ± 9 mol y -1 ) estimated in the current study, and that there may be limited net in-situ production and input of MMHg from river sediments. Watershed Contributions

46. u The Pettaquamscutt River Estuary (PRE; RI) is relatively remote from point sources with a watershed that can be characterized as rural/residential. u Scrupulously dated, varved sediment core (Lima et al., 2003/2005) provides a potentially valuable analog for assessing anthropogenic impact and temporal changes in Hg accumulation/inputs in the Harbor Estuary over the past half century. u Hg flux ratio (actual/preindustrial Hg accumulation) peaked in 1950 and 1960 at 12, but the ratio in 1997 was 4, representing a substantial decline in Hg inputs by about a factor of 3. Hg Accumulation in NY/NJ Harbor

47. u Sediment Hg accumulation fluxes are not available for the Harbor, but using sediment Hg concentrations (Bopp et al., 2006), approximate accumulation ratios can be estimated. u In the mid-1960s the actual/preindustrial Hg concentration ratio ranged from 13 (Jamaica Bay) to >100 (Arthur Kill), and were reduced to 3 to 27 in 1995/1996. u Therefore, there has been a decline in contaminant Hg inputs to the Harbor Estuary since the 1960s, and although difficult to provide a quantitative estimate, a factor of 3-5 is likely u Although there is substantially more Hg accumulating per unit area, the Harbor is comparable to the PRE where the decline in Hg accumulation was about 3. Hg Accumulation in NY/NJ Harbor (continued)