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Temporal Variation and Cycling of Trace Elements in The Temporal Variation and Cycling of Trace Elements in the Humboldt Bay Estuary Justin Martin1 and Matthew Hurst2 1 Department of Biological Sciences, Humboldt State University, Arcata CA 95521 Abstract 2 Department of Chemistry, Humboldt State University, Arcata CA 95521 The distribution of metals (manganese, iron, cobalt, nickel, copper, zinc, 600 80 Daily Rainfall (Fall 2007 - Fall 2008) cadmium, lead) and nutrients (nitrate, phosphate, silicate) was investigated 2.50 during 2007-2008 in the waters of Humboldt Bay. Samples were collected a. Mn b. Ni g. at the Humboldt Bay entrance during the incoming tide, Indian Island at 2.25 500 mid-tide, and Mad River Slough during the outgoing tide. The study 2.00 established background levels, identified contributing end members, and 60 Bay Entrance (Dissolved) Bay Entrance (Soluble) . 1.75 resolved the temporal variation of these trace elements in Humboldt 400 Indian Island (Dissolved) Indian Island (Soluble) Bay. The physical speciation of the metals was determined by separating 1.50 the water samples into particulate, colloidal and soluble fractions. The "First Flush" "First Flush" Mad River Slough (Dissolved) Mad River Slough (Soluble) metal data suggest that both runoff and resuspended sediments 300 40 1.25 Rainfall (in) Rainfall contribute to elevated levels of trace metals (except cadmium) in the 1.00 water column, with runoff during the winter months contributing Mn Concentration (nM) 200 to the highest dissolved metal concentrations. The contaminant Ni Concentration (nM) 0.75 20 metals (cobalt, nickel, copper, zinc, lead) delivered to Humboldt 0.50 Bay through freshwater inputs accumulate in the sediments and 100 are resuspended during spring wind events and subsequently 0.25 removed from the estuary through tidal action. Lead is 0 0 0.00 1 0.00 60.00 120.00 180.00 240.00 300.00 360.00 0.00 60.00 120.00 180.00 240.00 300.00 360.00 11 21 31 41 51 61 71 81 91 221 231 241 251 261 271 281 291 301 311 321 331 341 351 361 primarily associated with the particulate phase and can be Fall Winter Spring Summer Fall Fall Winter Spring Summer Fall Fall Winter 101 111 121 131 141 151 Spring161 171 181 191 201 211 Summer Fall used as a tracer of suspended sediments. Upwelled water entering Humboldt Bay is the primary source of cadmium c. 1.0 Average Wind Speed and Direction d. 25.00 (Fall 2007 - Fall 2008) with the highest concentrations found at the Bay entrance 15 Zn Cd during late spring. The nutrient data show that the 20.00 h. California coastal waters are the primary source of 0.8 nutrients to Humboldt Bay. Although anthropogenic 15.00 . sources of metals and nutrients exist, levels of these trace . 10.00 10 0.6 elements are well below other well-studied estuaries in the Northerly continental United States. 5.00 0.00 0.4 Methods --------------- -5.00 5 Zn ConcentrationZn (nM) -10.00 Unfiltered Sample ConcentrationCd (nM) 0.2 Southerly -15.00 0.03 µm (200kDa) flow-through filter -20.00 10 µm PCTE filter 0 0.0 -25.00 0.03 µm filtrate 0.00 60.00 120.00 180.00 240.00 300.00 360.00 0.00 60.00 120.00 180.00 240.00 300.00 360.00 Fall Winter Spring Summer Fall Fall Winter Spring Summer Fall Fall Winter Spring Summer Fall 15.0 e. 30.0 0.2 µm PCTE filter Co f. Cu Annual weather patterns appear to strongly control the temporal variation of metals in Humboldt UV-irradiation and chelating resin- Bay. Manganese, zinc, cobalt, and nickel (Figures a, b, c, & e) enter the bay primarily from land column partitioning (CRCP) 25.0 12.0 and this input is highest during the winter rains (Figure g). The annual trend of these metals varies with the annual trend in rainfall . Cadmium concentrations in Humboldt Bay varied with the occurrence of strong northerly winds as can be expected of elements entering the bay via upwelled . 20.0 0.2 µm filtrate . ocean water (Figures d and h). The influence of weather on copper is also evident, however, 9.0 internal sources within the bay contribute to elevated concentrations during mild weather MS-ICP-MS conditions (Figure f.). 15.0 Comparison of Dissolved Metal Concentrations in Humboldt Bay with other Estuarine Waters 6.0 Contaminant Humboldt San Francisco San Diego Galveston Narragansett Acetic acid 10.0 Trace Metal Bay Bay (1-2) Bay (3) Bay (4) Bay (5) Bomb digested in ConcentrationCu (nM) Co ConcentrationCo (nM) conc. HNO3 and HF leached Zn 2-22 4-48 NA 2-33 16-72 3.0 5.0 Cu 2-15 22-68 14-44 8-27 12-27 Co 0.2-6.0 0.4-5.3 0.5-2.4 0.4-10 NA The particulate (0.2-10 µm, > 10 µm) size-fractions were separated further into leachable (chemically AQQ labile) and refractory fractions. The difference in trace metal concentration between the soluble 0.0 0.0 Pb 0.01-0.03 0.05-1.4 0.1-0.2 0.04-0.5 NA µ µ µ 0.00Fall 60 . 00 Winter 120 . 00 Spring180.00 240 . 00Summer 300 . 00 Fa360ll . 00 0.00 Fall 60 . 00 Winter120 .00 Spring180.00 240 . 00 Summer 300 . 00 Fall360 . 00 (< 0.03 m) and dissolved (< 0.2 m) fractions operationally define the colloidal fraction (0.03-0.2 m). Cd 0.2-0.6 0.5-1.5 0.5-1.7 0.03-0.1 NA 1) Flegal A. R., Smith G. J., Gill G. A., Sañudo-Wilhelmy S., and Anderson L. C. D. (1991) Dissolved trace element cycles in the San Francisco Bay estuary. Mar. Bay Entrance (Dissolved) a Concentrations of metals in the dissolved and soluble phases at each of the three SLEW-3 Reference Material (ppb) Chem. 36, 329-363. Method Blank 2) San Francisco Estuary Institute (1993) Regional Monitoring Program Annual Report. study sites were determined every two weeks. All metal concentrations were b 3) Flegal A. R. and Sañudo-Wilhelmy S. (1993) Comparable Levels of trace metal contamination in two semi-enclosed embaymetns: Sand Diego Bay and South San Bay Entrance (Soluble) Element Measured Certified (nM) Francisco Bay. Environ. Sci. Technol. 27, 1934-1936. Results influenced by climate conditions, tidal action and location within the bay. Fe 0.593 ± 0.028 0.568 ± 0.059 1.7890±0.210 4) Wen, L.S., P.H. Santschi, C. Paternostro, and Gill G. (1998). Estuarine trace metal distributions in Galveston Bay. Marine Chemistry, 55, 129-152. Indian Island (Dissolved) Co 0.046 ± 0.004 0.042 ± 0.010 0.0840±0.013 5) Wells M. L., Smith G. J., and Bruland K. W. (2000) The distribution of colloidal and particulate bioactive metals in Narragansett Bay, RI. Mar. Chem. 71, 143-163. Dissolved Nitrate in Humboldt Bay Dissolved Phosphate in Humboldt Bay Manganese, zinc, cobalt, and nickel show increasing concentrations with increased 5050.0.0 Dissolved Nitrate in Humboldt Bay 88..00 Dissolved Phosphate in Humboldt Bay Cu 1.57 ± 0.04 1.55 ± 0.12 0.2740±.086 distance from the bay entrance (Figures a, b, c, & e). Cadmium exhibits the opposite Indian Island (Soluble) Zn 0.195 ± 0.033 0.201 ± 0.037 1.4200±0.182 4545.0.0 Bay Entrance Bay Entrance Bay Entrance Bay Entrance Cd ± ± ± Indian Island 77..00 Indian Island relationship (Figure d). Likewise, all of the metals except cadmium show increasing 0.051 0.002 0.048 0.004 0.009 0.001 4040.0.0 Mad River Slough Mad River Slough Mad River Slough (Dissolved) Mn 1.7± 0.6 1.61 ± 0.22 1.130±0.049 Indian Island Indian Island concentrations during the winter while Cadmium is highest in the spring (Figures a, 1215.0 Pb 0.0091±0.0015 0.0090±0.0014 0.0200±0.002 Conclusion 6.0 9.0 6.0 036.0 3535.0.0 Mad River Slough b, c, d, e, & f). Ni ± ± ± Mad River Slough 0.0060120.00180Mad.00240.00300.00 360River.00.00 Slough (Soluble) 1.23 0.05 1.23 0.07 2.3220 0.274 5.0 3030.0.0 5.0 Weather conditions (i.e., NW wind contributing to sediment resuspension, stormwater runoff) 2525.0.0 44..00 Dissolved and Soluble Cobalt vs. Salinity Total Lead vs. Turbidity play an important role in the concentrations of contaminant trace metals observed 2020.0.0 33..00 in Humboldt Bay. 15 1.2 15.0 15.0 Bay Entrance (Dissolved) Nitrate Concentration Nitrate Concentration (uM) Nitrate Concentration Nitrate Concentration (uM) 22..00 Bay Entrance (Dissolved) . 10.0 Phosphate Concentration (uM) 10.0 Phosphate Concentration (uM) Indian Island (Dissolved) Indian Island (Dissolved) The contaminant trace metal concentrations measured in Humboldt Bay were significantly less 5.0 11..00 Mad River Slough (Dissolved) 5.0 12 Mad River Slough (Dissolved) than the concentrations measured within other estuaries in the United States. 00.0.0 00..00 0.9 00.00.00Fall 60 60 . .00 00 Winter 120 120 ..00 00 Spring180180..00 240 . 00Summer 300 .. 00 Fall360360 ..00 00 0.00 60.00 120.00 180.00 240.00 300.00 360.00 Fall Winter Spring Summer Fall 0.00 FallFall 60 . 00 Winter Winter 120 . 00 Spring Spring180.00 240 . 00 Summer Summer 300 . 00 Fall Fall360 .00 . Nutrient data suggest that runoff from the Arcata Bottoms is a contributing source R² = 0.512 7070.0.0 DissolvedDissolved SilicateSilicate in Humboldt BayBay Nitrate, phosphate and silicate each exhibit 9 of nitrogen species, but is significantly less than the contributions of the Pacific Bay Entrance unique behavior within Humboldt Bay.
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