A chloride budget for Onondaga Lake,New York,U.S.A.

A Cl budget is presented for a 12 yr period (1970–1981) for Cl enriched (approximate volume-weighted average concentration of 1500 mg Cl L^?1) Onondaga Lake, New York. The budget utilizes continuous discharge and lake and stream water chemistry data, collected at an interval of approximately 2 weeks, over the 12 yr study period. Budget calculations are supplemented by high frequency water chemistry data from the lake and the tributary carrying the major portion of the loading. More than 85% of the external load of Cl (approximately 9 × 10⁸ kg yr^?1) to the lake originates from an alkali manufacturer. Export of Cl from the lake was highly correlated to outflow from the lake (R = 0.915, for a resolution of 1 mo). A good balance between estimated external loads and lake export was obtained (within 7%) for the 12 yr period, indicating that lake concentrations are consistent with external loading of this conservative substance. The results of this analysis contradict previous calculations that indicated 40 to 50% of the Cl in the lake originated from natural internal sources.     

Failure of spring turnover in Onondaga Lake,NY, U.S.A.

Onondaga Lake, N.Y., failed to turnover in the spring of 1986 because of the strong chemical stratification under the ice that developed as a result of ionic discharges from an alkali plant. This stratification had a negative impact on the O₂ resources of the lake, as the lower depleted layers of the lake were not replenished with O₂. Anoxia and anaerobiesis in the bottom water expanded following ‘ice-out’. Comparison of characteristics observed for the winter through spring interval of 1986 with historic data indicates Onandaga Lake has failed to experience spring turnover in a number of years (approximately 7 of the last 18 yr) because of the ionic discharges from the alkali plant.     

The density of inflows to Onondaga Lake,U.S.A., 1980 and 1981

The temporal distributions of the densities of inflows to Onondaga Lake were calculated for the spring to fall period of 1980 and 1981, and compared to the attendant density stratification in ion enriched Onondaga Lake. The industrial utilization of the lake resulted in substantial density differences between the inflows and the lake. Inflows carrying substantial fractions of industrial ionic waste were more dense than the lake, and at times plunged to stratified layers. Water withdrawn from the lower layers of the lake for industrial cooling was displaced to the upper layers as a result of heating. Dilute fluvial inflows were substantially less dense than the lake. The density differences between the inflows and the lake were largely responsible for the rather unique features of density stratification documented for the lake in 1980, and are probably of further importance in nutrient loading to, and cycling in, Onondaga Lake.     

Modifications in phosphorus loading to Onondaga Lake,U.S.A., Associated with alkali Manufacturing

The effects of an alkali production facility on P loading to the epilimnion of Onondaga Lake are documented for the spring to fall interval of 1980 and 1981. The effects include additional load to the epilimnion from the hypolimnion and the outlet, and reduced loads from dense, ion-enriched inflows. Despite the compensating effects, the load received by the epilimnion from spring through fall is greater than previously estimated as a result of the manufacturing operations.     

The distribution of nitrogen species in polluted Onondaga Lake,N.Y., U.S.A.

The temporal and vertical distributions of four N species, N0₃ ^?, NO₂ ^?, total ammonia (T-NH₃), and free ammonia (NH₃), are documented for Onondaga Lake, an urban, polluted, hypereutrophic, dimictic, lake that receives a very high load of T-NH₃. Nitrate and NO₂ ^? were lost rapidly from the hypolimnion, and T-NH₃ accumulated to high concentrations (maximum > 10 mgN L^?1), after the onset of anoxia, consistent with the lake's high level of productivity. The concentrations of T-NH₃, NH₃ and N0₃ ^? that were maintained in the epilimnion (average concentrations at a depth of 1 m of 2.81, 0.16 and 0.91 mgN L^?1, respectively), and concentrations of N0₂ ^? that developed in the epilimnion (maximum of 0.48 mgN L^?1), were high in comparison to levels reported in the literature. These elevated concentrations are largely a result of the extremely high loads of T-NH₃, and its precursors, received by the lake. Water quality problems in the lake related to the prevailing high concentrations of N species include potential toxicity effects and severe lake-wide oxygen depletion during fall turnover.     

Density stratification in ionically enriched Onondaga lake,U.S.A.

Denstity stratification was characterized in ionically enriched Onondaga Lake for a 7 mo period of 1980, based on paired profiles of temperature and cloride collected at 1 m depth intervals from a single deep water location on 54 different occasions. The lake was both thermally and chemically stratified. The chemical component represented 38.5% of the density stratification for the study period. It was most often the dominant component in establishing the depth of the upper mixed layer, which was unusually shallow in the lake. Further, the presense of the chemical component prolonged the stratification period. The chemical component of stratification decreased progressively through the study. The altered stratification characteristics of the lake may have negative effects on the level of biomass in the upper waters and the oxygen resources of the lower waters.     

Chloride in the pore water and water column of Onondaga Lake,N.Y., U.S.A.

The vertical distributions of Cl in the pore waters of the sediments and in the water column of Onondaga Lake, New York, are documented and used to estimate the diffusion flux of Cl across the sediment-water interface, and establish the reduction in lake concentrations that has occurred as a result of the closure of an industrial source of Cl. Despite the industrial enrichment of the water column with Cl over the last 100 yr, gradients within the upper sediments toward the overlying water of 6.9 to 8.5 × 10^?2 mg cm^?3 cm^?1 exist in the deep basins of the lake. These upwards gradients are apparently a manifestation of the salt deposits that underlie the region. The estimated diffusion flux from the sediments to the water column, 3.2 × 106 kg yr^?1, represents a small percentage of the external load during the operation of the industry (0.4%) and after its closure (1.6%). The Cl concentration has decreased approximately 70% in response to an approximately equal percent reduction in external loading, as a result of closure of the industry. This supports the position that the lake's concentrations largely reflect external loading and lake flushing associated with surface inputs.     

Distribution of mercury in the aquatic food web of Onondaga Lake,New York

Historical discharges of mercury (Hg) to Onondaga Lake, New York, have resulted in elevated Hg concentrations in lake fishes. In 1990, a remedial investigation and feasibility study (RI/FS) was initiated to evaluate problems related to Hg and other hazardous substances in the lake. As part of the RI/FS, the distribution of Hg in the aquatic food web was determined to provide input to a site-specific model of Hg cycling and to evaluate potential ecological risks of Hg in the lake. Mercury concentrations were measured in surficial sediments, sediment interstitial water, lake water, phytoplankton, Zooplankton, benthic macroinvertebrates, and fishes (including planktivores, benthivores, and piscivores). The percentage of total Hg accounted for by methyl-Hg (CH₃Hg) generally increased with higher trophic levels, confirming that CH₃Hg is more efficiently transferred to higher trophic levels than is inorganic Hg. Concentrations of total Hg in amphipods and chironomids were closely related to concentrations of total Hg in sediments, suggesting that sediments are a likely source of Hg for benthic macroinvertebrates. Mercury concentrations in edible muscle tissue (fillets) of lake fishes have declined substantially from values found in the early 1970s, reflecting the large reductions in Hg discharges to the lake that have occurred since that time. The CH₃Hg concentrations in fillets and whole bodies of fishes generally were similar, indicating that concentrations in fillets often can provide estimates of concentrations in whole bodies. Methyl-Hg concentrations and bioaccumulation factors increased with higher trophic levels in both the pelagic and benthic components of the lake food web.     

Depletion of epilimnetic oxygen and accumulation of hydrogen sulfide in the hypolimnion of Onondaga Lake,NY, U.S.A.

The depletion of epilimnetic DO during fall, and the accumulation of H₂S in the hypolimnion during summer, are documented for polluted hypereutrophic Onondaga Lake, NY, U.S.A. The fall epilimnetic DO depletion is so severe that in many, if not all years, the New York State standard for minimum DO of 4 mg- L^?1 is violated for periods as long as 1 mo. The depletion is caused by the transport of O₂ demanding species, particularly H₂S, from the hypolimnion into the epilimnion. Hydrogen sulfide accumulates progressively through the summer, mostly via SO _inf4 ^sup2? reduction, to unusually high concentrations; a maximum of 1.65 mM has been observed. These conditions are apparently manifestations of hypereutrophy, and thus may be subject to remediation through P management efforts.     

Seasonal variability in the Mercury speciation of Onondaga Lake (New York)

Dissolved and particulate Hg speciation was determined on four occasions in the Spring to Fall interval of 1989, at three depths of the water column of Onondaga Lake, New York; an urban system in which the sediments and fish flesh are contaminated with H_g. Species determined included total Hg (Hg_t), reactive (‘ionic’) Hg (Hg_i), monomethylmercury (CH₃HgX), elemental Hg (Hg°) and dimethylmercury (CH₃)₂Hg). Onondaga Lake was found to contain very high levels of Hg_t (2 to 25 ng L^?1 Hg), Hg_j (0.5 to 10 ng L^?1 Hg), and CH₃HgX (0.3 to 7 ng L^?1 Hg), which generally increased with depth in the lake. These concentrations represent a significant level of contamination, based upon comparisons with other polluted and pristine sites. Elemental Hg levels were typically about 0.05 ng L^?1 and (CH₃)₂Hg was near the limits of detection (?0.001 ng) L^?1 in most samples. The greatest CH₃HgX concentrations in the hypolimnion, as well as the largest gradients of both CH₃HgX and (Hg_t), were observed upon the first onset of stratification, in early summer. These concentrations did not become more pronounced, however, as stratification and H₂S levels in the hypolimnion increased throughout the summer. The very low concentrations of (CH₃)₂Hg in these MeHg and sulfide-rich waters calls into question the belief that CH₃HgX and H₂S will react to yield volatile dimethyl-mercury, which can then escape to the atmosphere by diffusion. Mercury speciation was highly dynamic, indicating active cycling within the lake, and an apparent sensitivity to changes in attendant Iimnological conditions that track the stratification cycle.     

Phosphorus cycling in ionically polluted Onondaga lake,New York

A synthesis of the P cycling in Onondaga Lake, New York, is presented, with particular emphasis on the impact of the attendant chemical pollution. The lake has been the focus of a restoration program aimed at reducing phytoplankton biomass through reduction of external P loads. The chemical pollution has altered the behavior of P in at least four ways: (1) reduced vertical mixing, (2) enhanced chemical reactivity of P, (3) increased rate of deposition of P, and (4) reduced availability of sedimentary P. These features reflect very nonconservative behavior of P in the lake, which should facilitate the positive response of the lake to further restoration efforts. The failure of Onondaga Lake to respond to major reductions in external P loading achieved by 1981 reflects the degree to which the system was originally overloaded. Internal P cycling, and P concentrations, in the lake would increase if the loading of ionic material from the major source was discontinued, due to the reversal of existing pollution-based alterations to the P cycle.     

Modeling Cl concentration in Cayuga Lake,U.S.A.

The annual average concentration of Cl in Cayuga Lake, NY, has decreased from a value of approximately 102 mg L^?1 in 1970, when the discharge of NaCl fines from an adjoining rock salt mine was discontinued, to a concentration of approximately 46 mg L^?1 in 1988. A complete-mixed model for Cl concentration accurately simulated this decrease in concentration, establishing that the decrease was the result of an abrupt reduction in loading. The time course of the decrease strongly supports the position that the high Cl concentrations that prevailed in the lake in the late 1960's were largely a result of the discharge from the mining facility, and not due to the input of enriched groundwater as previously hypothesized. The predicted steady-state Cl concentration associated with the complete flushing of the mining facility input, expected in about the year 2000, is approximately 32 mg L^?1. Further, the model analysis supports previous speculation that the major source of material loading to the lake, the Seneca River, ‘short-circuits’ to the outlet; i.e., this tributary should not be included in material budgets for the lake.     

Sediment Quality in Burlington Harbor,Lake Champlain,U.S.A.

Surface samples and cores were collected in 1993 fromthe Burlington Harbor region of Lake Champlain. Sediment samples were analyzed for trace metals(cadmium, copper, lead, nickel, silver and zinc),simultaneously extracted metal/acid volatile sulfide(SEM-AVS), grain size, nutrients (carbon and nitrogen)and organic contaminants (polycyclic aromatichydrocarbons (PAHs) and polychlorinated biphenyls(PCBs)). The concentrations of cadmium, copper,silver and zinc from the partial sediment digestion ofthe surface samples correlated well with each other(r ²>0.60) indicating that either a commonprocess, or group of processes determined the sedimentconcentrations of these metals. In an analysis of thespatial distribution of the trace metals and PAHs,high surficial concentrations were present in thesouthern portion of the Harbor. The trace metal trendwas strengthened when the concentrations werenormalized by grain size. A sewage treatment plantoutfall discharge was present in the southeasternportion of the Harbor at the time of this study and isthe major source of trace metal and PAH contamination. Evaluation of sediment cores provides a proxy recordof historical trace metal and organic inputs. Thepeak accumulation rate for copper, cadmium, lead, andzinc was in the late 1960s and the peak silveraccumulation rate was later. The greatestaccumulation of trace metals occurred in the late1960s after discharges from the STP began. Subsequentdeclines in trace metal concentrations may beattributed to increased water and air regulations. The potential toxicity of trace metals and organiccontaminants was predicted by comparing contaminantconcentrations to benchmark concentrations andpotential trace metal bioavailability was predictedwith SEM-AVS results. Surface sample results indicate lead,silver, ΣPAHs and ΣPCBs are potentially toxicand/or bioavailable. These predictions were supportedby studies of biota in the Burlington Harborwatershed. There is a clear trend of decreasing PAHand trace metal contaminant concentrations withdistance from the STP outfall.     

Chloride cycling in two forested lake watersheds in the west-central adirondack mountains,New York,U.S.A.

The chemistry of precipitation, throughfall, soil water, ground water, and surface water was evaluated in two forested lake-watersheds over a 4-yr period to assess factors controlling Cl^? cycling. Results indicate that Cl^? cycling in these watersheds is more complex than the generally held view of the rapid transport of atmospherically derived Cl^? through the excosystem. The annual throughfall Cl^? flux for individual species in the northern hardwood forest was 2 to 5 times that of precipitation (56 eq ha^?1), whereas the Na⁺ throughfall flux, in general, was similar to the precipitation flux. Concentrations of soil-water Cl^? sampled from ceramic tension lysimeters at 20 cm below land surface generally exceeded the Na⁺ concentrations and averaged 31 μeq L^?1, the highest of any waters sampled in the watersheds, except throughfall under red spruce which averaged 34 μeq L^?1. Chloride was concentrated prior to storms and mobilized rapidly during storms as suggested by increases in streamwater Cl^? concentrations with increasing flow. Major sources of Cl^? in both watersheds are the forest floor and hornblende weathering in the soils and till. In the Panther Lake watershed, which contains mainly thick deposits of till (>3 m), hornblende weathering results in a net Cl^? flux 3 times greater than that in the Woods Lake watershed, which contains mainly thin deposits of till. The estimated accumulation rate of Cl^? in the biomass of the two watersheds was comparable to the precipitation Cl^? flux.     

Catchment-Scale Variation in the Nitrate Concentrations of Groundwater Seeps in the Catskill Mountains,New York,U.S.A.

Forested headwater streams in the Catskill Mountains of New York show significant among-catchment variability in mean annual nitrate (NO₃ ^-) concentrations. Large contributions from deep groundwater with high NO₃ ^-concentrations have been invoked to explain high NO₃ ^-concentrations in stream water during the growing season. To determine whether variable contributions of groundwater couldexplain among-catchment differences in streamwater, we measuredNO₃ ^- concentrations in 58 groundwater seeps distributed across six catchments known to have different annual average streamwater concentrations. Seeps were identified based on release from bedrock fractures and beddingplanes and had consistently lower temperatures than adjacentstreamwaters. Nitrate concentrations in seeps ranged from neardetection limits (0.005 mg NO₃ ^--N/L) to 0.75 mg NO₃ ^--N/L. Within individual catchments, groundwaterresidence time does not seem to strongly affect NO₃ ^-concentrations because in three out of four catchments therewere non-significant correlations between seep silica (SiO₂) concentrations, a proxy for residence time, andseep NO₃ ^- concentrations. Across catchments, therewas a significant but weak negative relationship betweenNO₃ ^- and SiO₂ concentrations. The large rangein NO₃ ^- concentrations of seeps across catchmentssuggests: 1) the principal process generating among-catchmentdifferences in streamwater NO₃ ^- concentrations mustinfluence water before it enters the groundwater flow system and 2) this process must act at large spatial scales becauseamong-catchment variability is much greater than intra-catchmentvariability. Differences in the quantity of groundwater contribution to stream baseflow are not sufficient to account for differences in streamwater NO₃ ^- concentrationsamong catchments in the Catskill Mountains.     

Distribution of mercury in the sediments of Onondaga Lake,N.Y.

Sediment cores and surface grab samples were collected throughout Onondaga Lake, New York, to determine the concentrations and distribution of mercury (Hg) in the sediments. Horizontal distribution patterns show the effect of sediment focusing and localized sources, with generally low Hg concentrations in the littoral zone sediments, higher concentrations in the profundal sediments, and highest concentrations near known sources of Hg. Several cores were dated and reflect historical loading patterns, with low-level increases in Hg concentration starting in the early 1800s and a large increase in 1947 and decrease in 1970 related to the local chloralkali industry. These cores indicate that Hg has low mobility in profundal sediments and that the contaminated sediments are effectively being buried.     

100 Years of Pb Deposition and Transport in Soils in Champaign,Illinois, U.S.A.

In Illinois, atmospheric deposition is one major source of heavy metal inputs to agricultural land. The atmospheric Pb deposition and transport record in agricultural soils in Champaign, Illinois, was established by studying surface and subsurface soil samples collectedduring the past 100 years from the Morrow Plots on the campus of the University of Illinois at Urbana-Champaign. The Pb content in the soilsamples was measured and the Pb deposition fluxes were calculated. ThePb content in surface soils increased sharply in the first half of the20th century, and stayed invariant since. The maximum Pb flux from theatmosphere was estimated to be 27 (±14) μg cm^-2 yr^-1around 1940. The major pollution source for this increase probably was residential coal burning. It was estimated that in 50 yr, morethan 50% of the Pb input had been lost from the surface soils.     

Chemistry differences in two streams entering an acidic lake in the Adirondack Mountains,New York (U.S.A.)

Solution chemistry was measured in two major inlets, lake water column, lake outlet, and soils of the South Lake watershed in the Adirondack Mountains, New York. The east inlet had greater concentrations of H⁺, sulfate-S, and Al and smaller concentrations of base cations and silica than the west inlet (70, 116, 25, 90, 64 and 4, 99, 8, 228, 148 μeq L^?1 of H⁺ and sulfate-S, μmol L^?1 Al, μeq L^?1 total base cations and μmol L^?1 silica in east and west inlets, respectively). Concentrations of base cations in C horizon soil solutions (157 μeq L^?1 total base cations) were smaller and greater than west and east inlets, respectively. This suggests that water flowing into the west inlet contacted deeper mineral layers, whereas water reaching the east inlet did not. Lake and lake outlet concentrations were also intermediate between the two inlets, and the lake was acidic (pH 4.9 to 5.1) with relatively high total monomeric Al concentrations (8 to 9 μmol Al L^?1). The east inlet also had greater DOC concentrations than the west (0.38 and 0.24 μmol C L^?1, respectively), again indicating that soil solutions entering the east inlet passed through the forest floor but had more limited contact with deeper mineral layers in comparison with the west inlet. Differences between the streams are hypothesized to be related to contact of percolating solutions with mineral soil horizons and underlying glacial till, which provides neutralization of acidic solutions and releases base cations. This work indicates that processes controlling surface water acidification can be spatially quite variable over a small watershed.     

Application of the Regional Mercury Cycling Model (RMCM) to Predict the Fate and Remediation of Mercury in Onondaga Lake,New York

Onondaga Lake exhibits elevated concentrations of total mercury (HgT) and methyl-mercury (MeHg) in the water column, sediments and fish tissue due to industrial inputs, wastewater discharge and urban runoff. The steady-state Regional Mercury Cycling Model (RMCM) was calibrated to Onondaga Lake and applied to evaluate various remediation scenarios. Because of detailed data available for Onondaga Lake, the RMCM was effectively calibrated. Model predictions of water column and fish concentrations of Hg generally agreed with measured values. The model underestimated concentrations of Hg in sediments. Mass balance calculations show that inputs of HgT largely originate from tributary and wastewater inflows to the lake. In contrast, MeHg is largely derived from internal production. Model calculations suggest that elimination of Hg inputs from wastewater effluent and of drainage from a former chlor-alkali facility could greatly decrease Hg concentrations in fish tissue.     

Rainfall Concentrations and Wet Atmospheric Deposition of Phosphorus and Other Constituents in Florida,U.S.A.

Concentrations of phosphorus (P) and other constituents inweekly composited rain samples and concurrently acquired rainfallvolumes, collected from September 1992 through October 1993, wereused to estimate volume-weighted concentrations and wetatmospheric deposition rates, and compared to estimates fromprevious studies. Since this study’s purpose was to estimateregionally representative concentrations and rates of wetatmospheric deposition, sampling locations were chosen to avoidsites characterized by substantial local resuspension orrecycling phenomena. Significant differences were found in the wet deposition rates of calcium (Ca), magnesium (Mg), potassium (K), sodium (Na), hydrogen (H), and chloride (Cl) ions between sampling stationsin Florida. Consequently, statewide deposition rates and volume-weighted concentrations were estimated only for P, and fororthophosphate (PO₄), ammonium (NH₄), nitrate (NO₃) and sulfate (SO₄) ions that were not found to be spatially variable. Over the period of record, the mean rate of wet atmospheric P deposition across the state, and the mean rainfall P concentration, were found to be 25±>5 μg P M^-2 wk^-1 and 1.3±0.1 μg P L ^-1, respectively.