Speciation of trace metals in sediments of a tropical estuary

Axial surveys were performed in the two river tributaries of the Cochin estuary, SW India during November 1988. Surficial sediments were subjected to sequential chemical extractions to delineate five metal fractions, namely, exchangeable, carbonate bound, easily reducible, organic/sulfide bound, and residual. The results indicated selective accumulation of Mn and Ni in carbonate bound and organic/sulfide forms, along with marginal amounts of Co in the exchangeable fraction. Large portions of Fe and Cr occurred in the residual fraction, whereas composite fractionation of Zn species was noticed. The exchangeable fractions of Fe and Cr as well as of easily reducible cobalt were below detection limits. The levels of Cr and Zn indicate anthropogenic inputs in this estuary, whereas Co and Ni show regional contamination exceeding natural levels. The analytical speciation procedure helps to deduce the sedimental diagenetic processes in the estuarine environment.     

Heavy metals in sediments of a large, turbid tropical lake affected by anthropogenic discharges

 Bottom-water data and trace metal concentration of Cu, Cr, Ni, Pb, Co, Zn, and organic matter in surficial sediment samples from 13 sampling stations of Lake Chapala in Mexico were studied. The lake is turbid with a great amount of flocculated sediments as a result of wind mixing, sediment re-suspension, and Lerma River discharges. Al distribution pattern in sediments was used as an indicator of the Lerma River discharges into Lake Chapala. The highest values of Cu (33.27 ppm), Cr (81.94 ppm), Pb (99.8 ppm), and Zn (149.7 ppm) were detected in sediments near the lake outlet. The bioavailable metal fraction is low for all metals except Pb, which shows 65–93% of the total metal concentration in bioavailable form. The minimum energy zone in the lake was related to organic matter concentration and was located in the SE part of the lake. An analysis of the studied parameters shows two zones: eastern zone (fluvio-deltaic) and central-western zone (lacustrine). Received: 9 September 1998 · Accepted: 16 November 1998     

Spatial and temporal variation of heavy metals in a tropical estuary

The lower part of the Coatzacoalcos River has great industrial development in which high pollution has been reported. Surface sediments of this area were studied over a year to observe spatial and seasonal sedimentological and chemical variations. Higher metal concentrations were found during the dry season, Pajaritos Dock and Teapa sampling points showing the highest values. Ni (182 ppm) and Co (37 ppm) concentrations are elevated relative to other estuarine areas. Metal normalization against Al₂O₃ content shows contaminant input in areas where urban and industrial discharges exist. A cluster analysis of the data separates sediment samples from the different sampling trips, suggesting the dynamic nature of the sediments. Through the statistical t-test, metal enrichment of Cd, Cu, Cr, Ni, Pb, and Zn was evaluated and compared with metal concentration in sediments of the river higher parts. The percentage of bioavailable metals is a function of the physicochemical characteristics of the system.     

Distribution of colloidal trace metals in the San Francisco Bay estuary

The size distribution of trace metals (Al, Ag, Cd, Cu, Fe, Mn, Ni, Sr, and Zn) was examined in surface waters of the San Francisco Bay estuary. Water samples were collected in January 1994 across the whole salinity gradient and fractionated into total dissolved (<0.2 μm colloidal (10 KDa–0.2 μm) and < 10 kDa molecular weight phases. In the low salinity region of the estuary, concentrations of colloidal A1, Ag, and Fe accounted for ≥84% of the total dissolved fraction, and colloidal Cu and Mn accounted for 16–20% of the total. At high salinities, while colloidal Fe was still relatively high (40% of the dissolved), very little colloidal Al, Mn, and Cu (<10%) and no colloidal Ag was detectable. Colloidal Zn accounted for <3% of the total dissolved along the estuary, and colloidal Ni was only detectable (<2%) at the river endmember. All of the total dissolved Cd and Sr throughout the estuary consisted of relatively low molecular weight (<10 kDa) species. The relative affinity of metals for humic substances and their reactivity with particle surfaces appear to determine the amounts of metal associated with colloids. The mixing behavior of metals along the estuary appears to be determined by the relative contribution of the colloidal phase to the total dissolved pool. Metals with a small or undetectable colloidal fraction showed a nonconservative excess (Cd, Cu, Ni, and Mn) or conservative mixing (Sr) in the total dissolved fraction, relative to ideal dilution of river water and seawater along the estuary.

The salt-induced coagulation of colloidal A1, Fe, and Cu is indicated by their highly nonconservative removal along the salinity gradient. However, colloidal metals with low affinity for humic substances (Mn and Zn) showed conservative mixing behavior, indicating that some riverine colloids are not effectively aggregated during their transport to the sea. While colloidal metal concentrations correlated with dissolved organic carbon, they also covaried with colloidal Al, suggesting that colloids are a mixture of organic and inorganic components. Furthermore, the similarity between the colloidal metal:A1 ratios with the crustal ratios indicated that colloids could be the product of weathering processes or particle resuspension. Distribution coefficients for colloidal particles (K_c) and for large, filter-retained particles (K_d) were of the same magnitude, suggesting similar binding strength for the two types of particles. Also, the dependence of the distribution coefficients on the amount of suspended particulate matter (the so-called particle concentration effect) was still evident for the colloids-corrected distribution coefficient (K_p+c) and for metals (e.g., Ni) without affinity for colloidal particles.     

Pore water trace metal chemistry in polluted sediments of a tropical estuary of SE Brazil

The Sepetiba Bay is a shallow water body semi enclosed located on the west side of Rio de Janeiro City. Almost 80% of flesh water discharge, from the St Francisco canal, coming from the northern side of the bay develops an estuarine environment. Fishing and tourism are some of the most important economic activities in the area. During 35 years a zinc/cadmium smelter has polluted the bay. The objective of this investigation is to demonstrate the diagenetic processes and cadmium remobilization into pore water from the contaminated sediments. Two sites were selected to compare diagenetic processes. Site P1 is located next to domestic effluents discharge into the bay and approximately 20km away from the smelter. Site P2 is located near the same smelter and next to the Mazomba estuary, which is not influenced directly by domestic effluents. Peeper samplers of 25 cells with a resolution of 2.5 cm were deployed at both the sites. After a 3-weeks period of equilibrium, the pore waters were separated from the cells and analyzed immediately （within 24 h） for alkalinity, NH3 and reactive soluble phosphorus on a spectrophotometer. An ICP-AESΣH2S spectrometer was used to analyze Na, Mg, Li, Ba, Sr, Si, Fe and Mn. Total and labile dissolved Cd in pore waters were determined by differential-pulse stripping voltametry. The dissolved constituents in the pore waters have shown that the intensities of diagenetic reactions are different between sites. The reactions are stronger at site P1 site than at site P2, especially between 7.5 cm and 22.5 cm, which is evident by the organic rich sediment.     

Fine-scale responses of phytoplankton to freshwater influx in a tropical monsoonal estuary following the onset of southwest monsoon

In May of 2007, a study was initiated by the National Institute of Oceanography (NIO), Goa, India, to investigate the influence of monsoonal rainfall on hydrographic conditions in the Mandovi River of India. The study was undertaken at a location ∼2 km upstream of the mouth of this estuary. During the premonsoon (PreM) in May, when circulation in the estuary was dominated by tidal activity, phytoplankton communities in the high saline (35–37 psu) waters at the study site were largely made up of the coastal neritic species Fragilaria oceanica, Ditylum brightwellii and Trichodesmium erythraeum. During the later part of the intermonsoon (InterM) phase, an abrupt decline in salinity led to a surge in phytoplankton biomass (Chlorophyll a ∼14 mg m^− 3), of a population that was dominated by Thalassiosira eccentricus. As the southwest monsoon (SWM) progressed and the estuary freshened salinity and Chlorophyll a (Chl a) concentrations decreased during the MoN, Skeletonema costatum established itself as the dominant form. Despite the low biomass (Chl a <2 mg m^− 3), the phytoplankton community of the MoN was the most diverse of the entire study. During the postmonsoon (PostM), the increase in salinity was marked by a surge in dinoflagellate populations comprising of Ceratium furca, Akashiwo sanguinea, and Pyrophacus horologium.     

Depositional environment of mudflats and mangroves and bioavailability of selected metals within mudflats in a tropical estuary

Four sediment cores representing adjacent mudflat and mangrove sub-environments of middle estuary (Shastri) were analyzed for sand, silt, clay, and organic carbon. Total metal concentration of iron (Fe), manganese (Mn), nickel (Ni), zinc (Zn), chromium (Cr), copper (Cu), cobalt (Co), and lead (Pb) and chemical speciation of Fe, Mn, and Co on selected samples was also carried out on mudflat cores. The sediments in the upper middle estuary were found to be deposited under highly varying hydrodynamic energy conditions; whereas lower middle estuary experienced relatively stable hydrodynamic energy conditions with time. The tributary joining the river near the upper middle estuary is found to be responsible for the addition of enhanced organic carbon and metal concentrations. Speciation study indicated Fe and Co are from natural lithogenic origin while Mn is derived from anthropogenic sources. Higher Mn and Co than apparent effects threshold can pose a high risk of toxicity to organisms associated with these sediments.     

Doppler SODAR observations of the temperature structure parameter during monsoon season over a tropical rural station,Gadanki

Doppler SODAR (Sound Detection and Ranging) measurements over a tropical Indian station at National Atmospheric Research Laboratory (NARL), Gadanki (13.5°N, 79.2°E) during two consecutive monsoon seasons, 2007 and 2008, are investigated to study the influence of mechanically generated turbulence on temperature structure parameter (C_T²)_{\rm T}^{2}) in the convective boundary layer. Increase in the C_T²_{\rm T}^{2} is observed after the arrival of monsoon for both seasons. Contribution of vertical wind shear in horizontal wind component to C_T²_{\rm T}^{2} due to zonal winds is responsible for the increase observed in the temperature structure parameter which is inferred from the results obtained. C_T²_{\rm T}^{2} is found to be increased by an order of 2 in both the lower and upper altitudes, respectively. Magnitude of wind speed is reported to be doubled with the arrival of monsoon. It is also observed that, southwest monsoon wind modulates the day-to-day variations of wind pattern over this station during the onset phase of monsoon season. The lower variability observed at lower height is attributed to the complex topography surrounding this region.     

Dissolved and particulate trace metals and their partitioning in a hypoxic estuary: The Tanshui Estuary in Northern Taiwan

The distribution and partitioning of trace metals (Co, Cu, Fe, Mn, Ni, and Zn) between dissolved and particulate phases were studied in the Tanshui Estuary. The upper reach of the estuary is hypoxic and heavily polluted due to domestic and industrial discharges. The concentration ranges of dissolved and leachable particulate trace metals in the Tanshui Estuary were: Co: 0.3–6.1 nM, 1.8–18.6 mg kg⁻¹; Cu: 5–53 nM, 22–500 mg kg⁻¹; Fe: 388–3,364 nM, 1.08–6.67%; Mn: 57–2,914 nM, 209–1,169 mg kg⁻¹; Ni: 7–310 nM, 6–108 mg kg⁻¹; and Zn: 12–176 nM, 62–1,316 mg kg⁻¹; respectively. The dissolved concentrations of the metals were 2–35 times higher than the average values of the world river water. The distributions of dissolved and particulate studied metals, except Mn, in the estuary showed scattering, which could be attributed to the discharges from many industrial wastewater disposal works located in the upper tributaries. The daily input of dissolved metals from the disposal works to the Tanshui Estuary ranged from 0.1–0.4 tons. Dissolved Mn was nearly conservative in the region with salinity higher than 10 psu, while particulate Mn decreased in the region with salinity of 10–15 psu. The concentration increased significantly seawards, corresponding with the distribution of dissolved oxygen. The distribution coefficient (K_D) for Mn in the lower estuary was nearly three orders of magnitude higher than in the upper estuary. This phenomenon may be attributed to the diffusion of Mn from the anoxic sediment in the upper estuary and gradual oxidation into particulate Mn in the middle and lower estuary as the estuarine water became more oxygenated. The distribution coefficient for Cu decreased with increasing salinity. The percentages of trace metals bound by suspended particulate matter decreased in the following order: Fe>Zn, Cu>Co>Mn>Ni.     

Fractionation of phosphorus in the sediments of a tropical estuary

Fractionation of phosphorus in the sediments of the Cochin estuary situated along the southwest coast of India was studied by applying sequential chemical extraction. The different forms of phosphorus were estimated seasonally (premonsoon, monsoon, and postmonsoon) under eight different schemes. The major forms of phosphorus analyzed were exchangeable P, anion exchangeable P, carbonate-bound P, labile and resistant organic P, Fe and Al P, calcium-bound P, and hydrolyzable surplus P. Quantitatively, the above fractions in isolation or in combination vary in content due to chemoestuarine variability and seasonal fluctuations. Changes in speciation have been noted in association with salinity variations in the waterway, especially following enhanced river runoff during the monsoon. The chemical forms of the sediment-bound phosphorus in the northern parts of this estuary have been shown to be modified by nonpoint sources. Sediment P fractionation defines the role of chemical speciation of phosphates (as nutrients) and is indicative of the processes controlling the pathways of P into the coastal waters. The changes in the exchangeable P, together with marked regional variations in calcium-bound P, exemplify the complex estuarine variability of phosphorus. Enhanced amounts of exchangeable P mark its appearence in high saline waters, signifying the presence of biologically available nutrient phosphorus. The calcium-bound P and hydrolyzable surplus P show significant relation with sediment organic carbon and Fe whereas other forms do not exhibit any marked covariation. The Ca and Na NTA extraction scheme is very specific in its selectivity.     

Sedimentation in a tropical, microtidal, wave-dominated coastal-plain estuary

The Mono estuary is an infilled, microtidal estuary located on the wave-dominated Bight of Benin coast which is subject to very strong eastward longshore drift. The estuarine fill comprises a thick unit of lagoonal mud deposited in a ‘central basin’between upland fluvial deposits and estuary-mouth wave-tide deposits. This lagoonal fill is capped by organic-rich tidal flat mud. In addition to tidal flat mud, the superficial facies overlying the ‘central basin’fill include remnants of spits resting on transgressive/washover sand, an estuary-mouth association of beach, shoreface, flood-tidal delta and tidal inlet deposits, and a thin sheet of fluvial sediments deposited over tidal flat mud. After an initial phase of spit intrusion over the infilled central basin east of the present Mono channel, the whole estuary mouth became bounded by a regressive barrier formed from sand supplied by the Volta Delta during the middle Holocene eustatic highstand. Barrier progradation ceased late in the Holocene following the establishment of an equilibrium plan-form shoreline alignment that allowed through-drift of Volta sand to sediment sinks further downdrift. Over the same period, accretion, from fluvially supplied sediments, of the estuarine plain close to the limit of spring high tides, or, over much of the lower valley, into a fluvial plain no longer subject to tidal flooding, induced marked meandering of the Mono and its tidal distributaries in response to confinement of much of the tidal prism to these channels. The process resulted in erosion of spit/washover and regressive barrier sand, and in reworking of the tidal flat and floodbasin deposits. The strong longshore drift, equilibrium shoreline alignment and the year-round persistence of a tidal inlet maintained by discharge from the Mono and from Lake Ahémé have resulted in a stationary barrier that is reworked by a mobile inlet. The Mono example shows that advanced estuarine infill may result in considerable facies reworking, obliteration of certain facies and marked spatial imbrication of fluvial, estuarine and wave-tide-deposited facies, and confirms patterns of sedimentary change described for microtidal estuaries on wave-influenced coasts. In addition, this study shows that local environmental factors such as sediment supply relative to limited accommodation space, and strong longshore drift, which may preclude accumulation of sediments in the vicinity of the estuary mouth, may lead to infilled equilibrium or near-equilibrium estuaries that will not necessarily evolve into deltas.     

Transitions in the surface energy balance during the life cycle of a monsoon season

In this observational/diagnostic study, we illustrate the time history of some important parameters of the surface energy balance during the life cycle of a single monsoon season. This chronology of the surface energy balance portrays the differential equilibrium state from the preonset phase to the withdrawal phase. This includes an analysis of the time history of base variables such as soil moisture, ground temperature, cloud cover, precipitation and humidity. This is followed by an analysis of the components of the surface energy balance where we note subtle changes in the overall balances as we proceed from one epoch of the monsoon to the next. Of interest here is the transition sequence: preonset, onset, break, revival, break, revival and withdrawal during the year 2001. Computations are all illustrated for a box over central India where the coastal effects were small, data coverage was not sparse and where the semi-arid land mass changes drastically to a lush green area. This region exhibited large changes in the components of surface energy balance. The principal results pertain to what balances the difference among the incoming short wave radiation (at the earth’s surface) and the long wave radiation exhibited by the ground. That difference is balanced by a dominant sensible heat flux and the reflected short wave radiation in the preonset stage. A sudden change in the Bowen ratio going from>1 to <1 is noted soon after the onset of monsoon. Thereafter the latent heat flux from the land surface takes an important role and the sensible heat flux acquires a diminishing role. We also examine the subtle changes that occur in the components of surface energy balance between the break and the active phases. The break phases are seen to be quite different from the preonset phases. This study is aimed to illustrate the major importance of moisture and clouds in the radiative transfer computations that are central to the surface energy balance during each epoch. These sensitivities (of moisture and clouds) have major consequences for weather and climate forecasts     

Abundance and fractionation of Al,Fe and trace metals following tidal inundation of a tropical acid sulfate soil

Tidal inundation was restored to a severely degraded tropical acid sulfate soil landscape and subsequent changes in the abundance and fractionation of Al, Fe and selected trace metals were investigated. After 5 a of regular tidal inundation there were large decreases in water-soluble and exchangeable Al fractions within former sulfuric horizons. This was strongly associated with decreased soil acidity and increases in pH, suggesting pH-dependent immobilisation of Al via precipitation as poorly soluble phases. The water-soluble fractions of Fe, Zn, Ni and Mn also decreased. However, there was substantial enrichment (2–5×) of the reactive Fe fraction (Fe_R; 1 M HCl extractable) near the soil surface, plus a closely corresponding enrichment of 1 M HCl extractable Cr, Zn, Ni and Mn. Surficial accumulations of Fe(III) minerals in the inter-tidal zone were poorly crystalline (up to 38% Fe_R) and comprised mainly of schwertmannite (Fe₈O₈(OH)₆SO₄) with minor quantities of goethite (α-FeOOH) and lepidocrocite (γ-FeOOH). These Fe (III) mineral accumulations provide an effective substrate for the adsorption/co-precipitation and accumulation of trace metals. Arsenic displayed contrary behaviour to trace metals with peak concentrations (∼60 μg g⁻¹) near the redox minima. Changes in the abundance and fractionation of the various metals can be primarily explained by the shift in the geochemical regime from oxic–acidic to reducing-circumneutral conditions, combined with the enrichment of reactive Fe near the soil surface. Whilst increasing sequestration of trace metals via sulfidisation is likely to occur over the long-term, the current abundance of reactive Fe near the sediment–water interface favours a dynamic environment with respect to metals in the tidally inundated areas.     

Analysis of trace transition elements and heavy metals in fish otoliths as tracers of habitat use by American eels in the Hudson River estuary

Transition and heavy metals within the calcified otoliths of estuarine fishes may represent valuable tracers of environmental exposures, allowing inferences on natality, habitat use, and exposure to pollution. Accurate measurement of very low concentrations of these metals in otoliths by inductively coupled plasma mass spectrometry (ICP-MS) is often precluded by the interferences of predominant calcium matrix. We coupled a solid phase extraction procedure to an ICP-MS instrument to overcome the matrix problems and improve the limits of detection. To test this novel application and the utility of otolith transition and heavy metals as tracers of habitat use, otoliths of American eel (Anguilla rostrata) captured from 6 locations (George Washington Bridge, Haverstraw, Newburgh, Kingston, Athens, and Albany) throughout the Hudson River estuary were analyzed for site specific differences expected due to varying environmental exposure. Several trace elements, including Al, Bi, Cd, Co, Cu, Ga, Mn, Ni, Pb, V, and Zn, were selectively extracted from otolith solutions and preconcentrated on a microcolumn of chelating resin. The concentrations of all elements inA. rostrata otoliths were above the limits of detection that ranged from 0.2 ng g^?1 for Co to 7 ng g^?1 for Zn. Differences in the elemental composition of the otoliths among the groups were significant indicating different levels of exposure to environmental conditions. Discriminant analysis yielded an overall location classification rate of 78%. Al, Bi, Cd, Mn, Ni, and V contributed most to the discriminant function. Samples collected at George Washington Bridge showed 100% discrimination from other locations, and higher levels of many transition and heavy metals, consistent with higher exposure to these metals in the most polluted region of the Hudson River estuary.     

Temporal and spatial variability of trace metals in suspended matter of the Mandovi estuary,central west coast of India

Studies on the suspended particulate matter (SPM) in the Mandovi estuary, western India indicate that during the monsoon and pre-monsoon, the SPM increases, and the major and trace metals decrease from stations in the upstream to downstream of the estuary. SPM is consistently low at all stations during the post-monsoon. Trace metals (Cu, Ni, Zn, Cr, and Pb) show strong inter-relationships. They correlate well with Fe and Mn only during the monsoon. The concentrations of Cr, Cu, and Pb are high during the post-monsoon. Enrichment factors and I _geo values of metals indicate that Mn shows significant to strong pollution in all seasons, while Cr, Ni, and Zn during monsoon, and Cr during the post-monsoon show moderate pollution. SPM is controlled by the turbidity maximum, while major and trace metals are governed seasonally by a combination of river discharge, resuspension, spillage of Fe–Mn particulates, and anthropogenic contamination. Incursion of saline waters deep into the river channel during the dry season facilitates aggregation and settling of particulate-borne pollutants close to the discharge area, thereby keeping the estuarine waters free from major contamination.     

The transport of Osmium and Strontium isotopes through a tropical estuary

We have determined the concentration and isotopic composition of Os and Sr in the estuarine waters from the Godavari delta in Peninsular India. Additionally, we have obtained the concentration and isotopic composition of Os and Al concentration in selected suspended particulate matter recovered on 0.45 μm filters. The Na, K, Mg, and Ca concentrations of water samples obtained along salinity gradients from two distributary channels in the delta display a general two component mixing between river- and sea-water. The data also reveal that Al behaves non-conservatively and is affected by interactions with suspended particulates. The ⁸⁷Sr/⁸⁶Sr ratio of the riverine end member is 0.716303 and shows a linear decrease with salinity to seawater value and Sr isotope systematics indicate that its behavior is conservative in the estuary.The ¹⁸⁷Os/¹⁸⁸Os ratio of the Godavari river end-member is 1.24 and within error of the average eroding upper continental crust. The concentration and isotopic composition of Os through the two salinity transects shows that its behavior in the Godavari estuary is complex and non-conservative. By comparing the Al/Os ratios and Os isotopes in the waters with those of the suspended particulate we find that both Os gains and losses occur in the water column. However, in one of the distributaries (Vasishta) the Os concentration of suspended load increases and that of dissolved load decreases with increasing salinity towards the Bay of Bengal end-member. We infer that there is removal of seawater Os at higher salinities. The estimated mean residence time of Os in the oceans is 37 ± 14 (2σ) kyr. A comparison of the Os concentration of the Bay of Bengal and the Indian Ocean waters indicates that the rainout rate of Os in Bay of Bengal is 30% faster than that in the open ocean and suggests that the observed discrepancy between the mean residence time calculated from mass balance considerations and that estimated from the relaxation of the Os isotopic ratio in marine record may not be real as the relaxation time experiments likely estimate the residence time for a basin/sub-basin and not for the entire ocean.     

Sediment budget-based estimates of trace metal inputs to a Chesapeake estuary

This article evaluates whether a sediment budget for the South River, Maryland, can be coupled with metals data from sediment cores to identify and quantify sources of historic metal inputs to marsh and subtidal sediments along the estuary. Metal inputs to estuarine marsh sediments come from fluvial runoff and atmospheric deposition. Metal inputs to subtidal sediments come from atmospheric deposition, fluvial runoff, coastal erosion, and estuarine waters. The metals budget for the estuary indicates that metal inputs from coastal erosion have remained relatively constant since 1840. Historical variations in metal contents of marsh sediments have probably resulted primarily from increasing atmospheric deposition in this century, but prior to 1900 may reflect changing fluvial sources, atmospheric inputs, or factors not quantified by the budget. Residual Pb, Cu, and Zn in the marsh sediments not accounted for by fluvial inputs was low to moderate in 1840, decreased to near zero circa 1910, and by 1987 had increased to levels that were one to ten times greater than those of 1840. Sources of variability in subtidal cores could not be clearly discerned because of geochemical fluxes, turbulent mixing, and bioturbation within the cores. The sediment-metal budgeting approach appears to be a viable method for delineating metal sources in small, relatively simple estuarine systems like the South River and in systems where recent deposition (for example, prograding marshes) prevents use of deep core analysis to identify background levels of metal. In larger systems or systems with more variable sources of sediment and metal input, however, assumptions and measurement errors in the metal budgeting approach suggest that deep core analysis and normalization techniques are probably preferable for identifying anthropogenic impacts.Field and laboratory research conducted at the Department of Geography, University of Maryland, College Park, Maryland, 20742, USAField and laboratory research conducted at the Marine and Estuarine Environmental Science Program, University of Maryland, College Park, Maryland, 20742, USA