Trace element accumulation in the tissues of fish from lakes with different pH values

Two species of fish, omnivorous Catostomus commersoni (white suckers) and carnivorous Perca flavescens (yellow perch) were collected from three natural lakes with different pH ranges (circumneutral, pH 6.5 to 6.8; variable, pH 5.8 to 6.7; and acidic, pH 4.9 to 5.4). The lakes are located in the North Branch of the Big Moose River drainage system in the New York State Adirondack Park Preserve. Concentrations of potentially toxic elements (Al, Cd, Cu, Ph, and Se) were measured by electrothermal atomic absorption spectrophotometry in water, sediment and fish (bone, gill, kidney, liver and muscle) from each lake. The results showed that concentrations of Pb and Cd were significantly higher (P < 0.05) in some of the tissues of the fish collected from the acidic lake. Also, the yellow perch from the acidic take had significantly higher (P<0.05) Se concentrations in their muscle and livers than fish from the other lakes. The concentrations of Al were elevated in the gill tissues of both fish species from the acidic lake relative to fish from the other lakes. Possible mechanisms contributing to these differences in tissue concentration are discussed.     

Trace element concentrations in fish from three Adirondack lakes with different pH values

Concentrations of 29 elements were detected in the axial muscle, and 44 elements were detected in the gut contents of white suckers (Catostomus commersoni) and yellow perch (Perca favescens) from three lakes located in the New York State Adirondack Preserve. The study lakes were acidic Darts Lake, variable pH Lake Rondaxe, and circumneutral Moss Lake. For the majority of the elements, there were no clear differences in the muscle concentrations among fish inhabiting the three types of lakes. Two notable exceptions were Hg and Pb. With some exceptions, the highest muscle tissue Pb concentrations were found in fish from the acidic lake. For both species, the Hg was higher in the muscle than in the gut regardless of lake acidity. Other elements potentially toxic to humans (As, Cd, Ga, Pb, Se, and TI) were not accumulated in the muscle relative to the gut.     

The role of dissolved organic carbon in the chemistry and bioavailability of mercury in remote Adirondack lakes

A number of recent studies have documented elevated concentrations of mercury (Hg) in fish caught in remote lakes and a pattern of increased concentrations of Hg in fish tissue with decreasing water column pH. Because of the potential linkage between fish Hg and surface water acidification, factors regulating water column concentrations and bioavailability of Hg were investigated in Adirondack lakes through a field study and application of the Mercury Cycling Model (MCM). Concentrations of total Hg and total MeHg were highly variable, with concentrations of total MeHg about 10% of total Hg in lakes which did not show anoxic conditions. In lakes exhibiting anoxic conditions in the hypolimnion during summer stratification, concentrations of total MeHg were elevated. Concentrations of total Hg and total MeHg increased with decreasing pH in remote Adirondack lakes. However, more importantly, concentrations of total Hg and total MeHg increased with increasing concentrations of dissolved organic carbon (DOC) and percent near-shore wetlands in the drainage basin. Mercury concentrations in muscle tissue of yellow perch from Adirondack lakes were elevated above the U.S. FDA action level (1 μg/g Hg) in 7% of the fish sampled or in one or more individual fish from 9 of the 16 lakes sampled. Fish Hg concentrations generally increased with increasing fish length, weight and age. Patterns of increasing Hg concentration with age likely reflect shifts in prey of yellow perch and the bioconcentration of Hg along the food chain. For age 3 to 5 perch, concentrations of Hg increased with increasing concentrations of DOC and percent near-shore wetlands in the drainage basin. However, for a lake with very high DOC concentrations, fish concentrations of Hg declined. Calculations with the MCM also show that concentrations of Hg species increase with increasing DOC due to complexation reactions. Increases in DOC result in increasing concentrations of Hg in biota but decreases in the bioconcentration factor of Hg in fish tissue. This research suggests that DOC is important in the transport of Hg to lake systems. High concentrations of DOC may complex MeHg, diminishing its bioavailability. At high concentrations of monomeric Al, the complexation of MeHg with DOC apparently decreases, enhancing the bioavailability of MeHg.     

Metal concentration in the gill,gastrointestinal tract,and carcass of white suckers (Catostomus commersoni) in relation to lake acidity

Adult white suckers were collected from four lakes in Maine that ranged in pH from 7.0 to 5.4. The gastrointestinal tract and remainder of the carcass of fishes of similar age and size from each lake, and gills from additional fishes of similar size, were analyzed for Al, Cd, Pb, and Zn. Carcasses were also analyzed for Hg. Concentrations of Al, Cd, and Pb were highest in the gastrointestinal tract and lowest in the carcass; Zn concentration was highest in the gill. For carcass, all metals except Al differed significantly among lakes, for gill tissue Cd and Pb differed, and for gastrointestinal tract, only Cd differed among lakes. Where differences were significant, patterns among lakes were similar in each tissue analyzed. Concentrations of Cd, Hg, and Pb were negatively correlated with lake water pH, acid neutralizing capacity (ANC), Ca, and lake:watershed area, and positively correlated with lake water SO₄, indicating that concentrations were higher in fish from more acidic lakes. Zinc concentrations in gills were unrelated to lake acidity, and carcass concentrations were higher in the less acidic lakes, which is the opposite of the pattern for the other metals studied. Zinc in gastrointestinal tract did not differ among lakes. Although the lakes we studied were located in undisturbed watersheds and did not receive any point source discharges, fish metal concentrations were comparable to or higher than those reported from waters receiving industrial discharges.     

Concentrations of trace elements in yellow perch (Perca flavescens) from six acidic lakes

Yellow perch (Perca flavescens) were collected from six small acidic lakes in northwestern New Jersey. Analyses of muscle tissue identified a pattern of increased concentrations of Hg in fish from the most acidic lakes; levels of Cd and Pb were greatly elevated in livers of specimens from two of the most acidic lakes. At one site, Sunfish Pond, positive correlations between fish size and Hg levels in muscle and Cd concentrations in livers were detected. In only one case did Hg concentrations in muscle tissue exceed the U.S. FDA action level of 1 μg g^?1 (wet wt).     

A review of the chemical record in lake sediment of energy related air pollution and its effects on lakes

Inter-lake variation in accumulation rates of energy-related elements is a function of gross sedimentation rate (sediment focusing), position on pollution gradients, and water chemistry. Accumulation rates of Pb in lake sediments from profundal area cores in the Adirondack Mountains of New York and northern New England range from 0.1 to 0.2 ug/cm²/y (pre-1800 A.D.) to as much as 2 μg/cm²/y (recent sediment). Rates increase from the late 1800's to nearly the present, in parallel. Accumulation rates for V remain at background values which range up to 0.5 ug/cm²/y and increase 5 to 10 × background in Adirondack Mountain lakes. Chronically acidic lakes have a subsurface maximum. Of these three metals, only Pb has elevated deposition rates in high elevation lakes in the Rocky Mountains of Colorado. Mining activity is believed responsible for the implied air pollution there.     

Mercury concentrations in northern pike,Esox lucius L., in small lakes of Evo area,southern Finland

We measured Hg concentrations in northern pike (Esox lucius) from 17 small lakes in Evo forest area, Lammi, southern Finland. The mean Hg concentration in muscle tissue of a 1 kg pike ranged from 0.15 to 1.36 μg g⁻¹ (ww) in the lakes. There was a trend towards higher concentrations in acidic and humic lakes than in circumneutral and clear-water lakes. The Hg content of pike from successive lakes of a lake chain was similar, whereas there were clear differences in the Hg concentrations among seepage lakes and the uppermost lakes of other lake chains. The latter was probably due to special characteristics of the lakes: in one lake pike was the only fish species, two of the lakes were regulated by beaver, and one lake was a groundwater or spring lake. Our observations indicate that Hg concentrations in pike can vary considerably from lake to lake in a small geographical area and that the variation among lakes in the accumulation of Hg in fish largely depends on lake characteristics and on the diet of pike.     

Trace Elements in Fish Overlying Subaqueous Tailings in the Tropical West Pacific

From 1972–1989, Bougainville Copper Limited (BCL) dischargedmine tailings into Empress Augusta Bay on the west coast ofBougainville Island, Papua New Guinea. For a decade(1977–1987), trace elements (Cu, Pb, Zn, Cd, Hg and As) weremeasured in muscle tissue and organs of 8 species of tropicalmarine fish common to both the east and west coasts of theIsland. Metal concentrations were not elevated in muscle tissueof west fish compared with those from the east coast.Concentrations of Cu, Pb, Zn and Cd in fish muscle from bothcoasts ranged from 10–15% of recommended maximum residuelimits (MRLs), whereas concentrations of Hg in muscle wereslightly higher, ranging up to 80% of the MRL (0.5 mgkg^-1 Hg wet wt.). Maximum total As concentrations (3.6 mgkg^-1 wet wt.) were recorded in the shark (Rhizoprionodon acutus), while highest Hg values (0.76 mgkg^-1 wet wt.) were found in hammerhead sharks (Sphyrnalewini) from both coasts. Despite significant temporalvariations in Hg and As concentrations in muscle tissue of somewest coast fish populations (p < 0.05), there was no evidencefor bioaccumulation or biomagnification of any of these metalsduring the 10 yr period, even in the soft organs (liver andkidney) of fish. Several site specific factors contributing toabsence of metals uptake from tailings are discussed.     

Metal concentration and calcification of bone of white sucker (Catostomus commersoni) in relation to lake pH

The concentrations of 17 elements were determined in the bone of white suckers (Catostomus commersoni) netted from 5 acid (pH range 4.8 to 5.8) and 2 circumneutral (pH=6.2 and 6.3) lakes in south-central Ontario. The bone Ca:P dry weight ratios were similar (2.0:1) for all fish populations except those of George Lake (pH=4.8) which showed a significantly lower Ca:P ratio (1.9:1, P < 0.05). Magnesium was also lower in the bone of these fish and in fish from 2 other acid lakes. Only bone Ba and S concentrations in the 7 fish populations correlated significantly to lake pH (R=?0.9 and R=?0.8, respectively, P < 0.05). Bone Mn concentrations correlated to dissolved lake Mn concentrations (R=0.8, P < 0.05), and was 7 fold greater in the bone of fish from George Lake and 2 fold greater in King Lake (pH=5.0) fish, vs fish from the 2 circumneutral lakes. Bone Zn was significantly greater in white sucker from George Lake, and tended to be higher in this species from King Lake, compared to all other fish populations. Bone concentrations of Fe, Cu, Ni and A1 showed no apparent trends among the 7 fish populations. Cd, Co, Cr, Mo, V and Be were not detected. The occurrence of a reduced Ca:P ratio coincident with the highest concentrations of Mn, Zn and Ba in the bone of fish from the most acidified environment suggests that increased metal concentrations which occur in surface waters coincident with lake acidification may affect bone calcification.     

Mercury in the surface water of Swedish forest lakes —concentrations,speciation and controlling factors

Concentrations of total Hg and five operationally defined Hg species were determined in the surface water of 25 Swedish forest lakes of different type. Regional and seasonal variations were studied during the ice-free season of 1986. The concentration of total Hg was usually in the range of 2 to 10 μg m-3. Hg concentrations were highly correlated to the concentration of humic matter measured as water color. Hg concentrations were about twice as high in acidic lakes (pH 5) than in circumneutral lakes, which is attributed basically to the acidity of humic compounds acting as Hg carriers in boreal waters. Significant seasonal variations were caused by hydrological processes. During periods of high water flow, Hg concentrations increased dramatically, especially in humic lakes. Between spring and autumn, chemically reactive Hg compounds were gradually replaced by more inert species. Hg/C ratios were higher than in surface runoff from forest watersheds, indicating a significant impact of direct deposition of Hg on lake surfaces during summer. Regional differences were small despite differences in Hg contamination.     

Aluminum toxicity to fish in acidic waters

An important consequence of acidification is the mobilization of Al from the edaphic to the aquatic environment. Elevated Al levels in acidic waters may be toxic to fish. Eggs, larvae, and postlarvae of white suckers (Catostomus commersoni) and brook trout (Salvelinus fontinalis) were exposed in laboratory bioassays to pH levels 4.2 to 5.6 and inorganic Al concentrations of 0 to 0.5 mg l^?1. Aluminum toxicity varied with both pH and life history stage. At low pH levels (4.2 to 4.8), the presence of Al (up 0.2 mg l^?1 for white suckers; 0.5 mg l^?1 for brook trout) was beneficial to egg survival through the eyed stage. In contrast, Al concentrations of 0.1 mg l^?1 (for white suckers) or 0.2 mg l^?1 (for brook trout) and greater resulted in measurable reductions in survival and growth of larvae and postlarvae at all pH levels (4.2 to 5.6). Aluminum was most toxic in over-saturated solutions at pH levels 5.2 to 5.4. The simultaneous increase in Al concentration with elevated acidity must be considered to accurately assess the potential effect of acidification of surface waters on survival of fish populations.     

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.     

The chemical responses of acidic Woods Lake,NY to two different treatments with calcium carbonate

A study was conducted to compare and contrast two approaches to neutralize an acidic lake by CaCO₃ addition (Woods Lake, Adirondack Mountains, New York, U.S.A.; 42°52′ N, 71°58′ W); direct water column treatment and treatment of both the water column and sediment. The latter treatment strategy was designed to release a slow, diffusive Ca²⁺. flux across the sediment/water interface and thereby delay the rate of reacidification. Both applications satisfactorily increased the acid neutralizing capacity (ANC) and Ca²⁺ of the lake, temporarily buffering the water column pH against acidic inputs from the watershed. The water column/sediment application involved a greater (50% more) dose in order to accomplish sediment treatment and resulted in a prolonged period of positive ANC in the water column. However, both treatments neutralized approximately the same quantity of runoff and equivalence of acidic inputs. Water column/sediment treatment may be an effective approach to help delay reacidification in shallow lakes of moderate hydraulic retention times. Unfortunately, many acidic Adirondack lakes have very short hydraulic retention times (<0.5 yr) and may not be neutralized for adequate durations by either water column or water column/sediment CaCO₃ treatments.     

Predicting Recovery from Acidic Deposition: Applying a Modified TAF (Tracking and Analysis Framework) Model to Maine (USA) High Elevation Lakes

We adapted a reduced-form model, built to predict the aquatic effects of alternative nitrogen and sulfur emissions scenarios on Adirondack lakes, New York, for use on high elevation lakes of Maine (HELM), USA. The Tracking and Analysis Framework (TAF) model was originally designed to evaluate the biotic, economic, and health effects of acid deposition. The TAF model developed in our study was used to assess the biotic effects of different levels of sulfate deposition resulting from alternative emissions scenarios. The aquatic portion of the model is based on a lumped-parameter watershed chemistry model, MAGIC (Model of Acidification of Groundwater in Catchments). The original TAF model was built by calibrating MAGIC to 33 lakes in the Adirondack Mountains. We calibrated MAGIC to 78 HELM lakes, and built reduced-form models from these MAGIC predictions. We evaluated TAF predictions of acid neutralizing capacity (ANC), a fish acid stress index (ASI), and the probability of fish presence in 2030 for four different SO₂ emissions-reduction scenarios. The most dramatic emissions reduction scenario produced only modest increases in mean ANC (16.8 μeq/L ± 7.9 μeq/L) and slight increases in mean predicted probability of presence of acid-sensitive fish (0.07± 0.09) across all lakes. However, a small number of lakes were predicted to have more substantial increases in ANC and improvements in other conditions for acid-sensitive fish. Our results reflect the reality that many of the high elevation lakes of Maine historically had low ANC and that some were even acidic in pre-industrial times. Thus, ’recovery’ for most of the high elevation lakes of Maine will be modest under any scenario of reduced acidic deposition.     

Assessment of the Extent to Which Intensively-studied Lakes are Representative of the Adirondack Region and Response to Future Changes in Acidic Deposition

Many lakes in the Adirondack Mountains, New York, have acidified over the past century due to acidic atmospheric deposition. More recently, most monitored lakes have shown signs of chemical recovery (increase in acid neutralizing capacity) as sulfur deposition levels have declined in response to the Clean Air Act and other emissions control legislation. We used measured and modeled trends in past lakewater acidification and projections of future recovery from acidification to extrapolate results from judgment samples of intensively studied lakes to the population of acid-sensitive Adirondack lakes. Simulations were developed for 70 watersheds using the Model of Acidification of Groundwater in Catchments (MAGIC) to classify lakes according to their sensitivity to change in atmospheric S and N deposition. MAGIC simulations suggested that the modeled Adirondack Long-Term Monitoring Project (ALTM) and Adirondack Effects Assessment Project (AEAP) lakes were largely among the lakes in the population that had acidified most between 1850 and 1990. Most of the modeled ALTM/AEAP lakes were within the top 36% of acid sensitivity, based on model projections of past acidification and future chemical recovery, compared with the 1,829 Adirondack lakes in EPA’s Environmental Monitoring and Assessment Program (EMAP) statistical frame. Results of this research will allow fuller utilization of data from on-going chemical and biological monitoring and process-level studies by providing a basis for regionalization of findings and developing/refining relationships among watershed characteristics, chemical change, and biological responses to changing levels of acidic deposition.     

Fluxes,pools, and turnover of mercury in Swedish forest lakes

In boreal forest lakes, high Hg concentrations in fish are common, even in remote areas. In this paper, the effects of atmospheric Hg pollution in Sweden are synthesized and related to a concept based on the strong interaction of Hg with biogenic matter (Hg/B). Based on this concept, a compartment model is developed to predict concentrations, pool sizes, flux rates and turnover times of Hg along the biogeochemical cycle, including atmosphere, forest soils, surface runoff, lake waters, and aquatic biota. The aim is to provide a conceptual framework, both for a comprehensive mechanistic model, and for predictions from readily available information, such as regional data on acid deposition, air temperature and surface runoff, and local data on the trophic status of lakes with respect to humus and nutrient concentrations. The model is in good agreement with observations from recent Swedish field studies in all compartments. It suggests a strong influence of climate on the susceptibility of soil and lake ecosystems in the boreal region to Hg contamination. The high Hg concentrations in fish from forest lakes can be largely attributed to the low productivity of both terrestrial and aquatic biota. The impact of historical point sources of Hg is considered, as well as the slow turnover of Hg in forest soils, both resulting in elevated fish Hg levels in humic lakes for centuries following atmospheric deposition.     

The coupling of mercury and organic matter in the biogeochemical cycle — towards a mechanistic model for the boreal forest zone

In boreal forest lakes, high Hg concentrations in fish are common, even in remote areas. In this paper, the effects of atmospheric Hg pollution in Sweden are synthesized and related to a concept based on the strong interaction of Hg with biogenic matter (Hg/B). Based on this concept, a compartment model is developed to predict concentrations, pool sizes, flux rates and turnover times of Hg along the biogeochemical cycle, including atmosphere, forest soils, surface runoff, lake waters, and aquatic biota. The aim is to provide a conceptual framework, both for a comprehensive mechanistic model, and for predictions from readily available information, such as regional data on acid deposition, air temperature and surface runoff, and local data on the trophic status of lakes with respect to humus and nutrient concentrations. The model is in good agreement with observations from recent Swedish field studies in all compartments. It suggests a strong influence of climate on the susceptibility of soil and lake ecosystems in the boreal region to Hg contamination. The high Hg concentrations in fish from forest lakes can be largely attributed to the low productivity of both terrestrial and aquatic biota. The impact of historical point sources of Hg is considered, as well as the slow turnover of Hg in forest soils, both resulting in elevated fish Hg levels in humic lakes for centuries following atmospheric deposition.     

Human exposure to mercury may decrease as acidic deposition increases

It has been hypothesized that human mercury (Hg) exposure via fish consumption will increase with increasing acidic deposition. Specifically, acidic deposition leads to reduced lake pH and alkalinity, and increased sulphate ion concentration ([SO₄ ^2?]), which in turn should cause increased Hg levels in fish, ultimately resulting in increased human Hg exposure via fish consumption. Our empirical test of this hypothesis found it to be false. We specifically examined Hg levels in the hair of Ontario Amerindians, who are known consumers of fish from lakes across the province, and observed a weak negative association with increasing sulphate deposition. An examination of Hg levels in lake trout, northern pike and walleye, three freshwater fish species commonly consumed by Ontario Amerindians, found a similar weak negative association with increasing sulphate deposition. Further analysis of these fish data found that fish [Hg] was most significantly (positively) associated with lake water concentrations of dissolved organic carbon (DOC), not pH, alkalinity or [SO₄ ^2?]. Lake DOC levels are lower in regions of greater acidic deposition. We propose an alternate hypothesis whereby human Hg exposure declines with increasing acidic deposition. In particular, we propose that increasing sulphate deposition leads to reduced lake DOC levels, which in turn leads to lower Hg in fish, ultimately reducing human Hg exposure via fish consumption.     

Evidence of fish population responses to acidification in the Eastern United States

The hypothesis that acidification has reduced or eliminated fish populations in certain areas of the eastern United States was investigated by examining present and historical fishery survey records. The causes of acidification (e.g., atmospheric deposition) were not specifically considered, although instances of obvious alternative explanations (e.g., acid mine drainage, organic acids) were avoided. The number of usable data sets located was small. Trend analyses are severely limited by the lack of high quality historical data. The strongest evidence for fisheries declines associated with acidification is provided by data for the Adirondack Mountain region of New York. In some lakes, fish populations have declined or disappeared; lakes experiencing fishery declines are now acidic. Alternative explanations for changes in fish communities over time were examined. In 49 lakes, some or all fish populations have apparently been lost with no available explanation other than acidification. Extrapolation of these data to the entire Adirondack Mountain region suggests that perhaps 200 to 400 lakes may have lost fish populations as a result of acidification. Streams in Pennsylvania and Massachusetts also had documented declines in fish populations that were associated with acidity; however, the data are fewer and less complete than those for New York. Acidification effects on fishery resources in other regions of the eastern United States are apparently minimal. The extent of the damage to date appears small relative to the total resource.