Controlled experimental acidification of lake sediments and resulting trace metal behavior

Severe stream water acidification occurs at higher altitudes (> 600 m a.s.l.) in the Western Harz mountains in Northern Germany. Since 1986 an interdisciplinary research team has followed the fate of pollutants in the 50 km² catchment of an important drinking water reservoir (Lake Söse). An acidification experiment has estimated the role of the remobilization of selected elements from the lake sediments via acidification. Aquaria were used to monitor the effects of a stepwise acidification (from the natural pH of 6.5 to 5.0, 4.0 and 3.0) of the water column over a reconstituted sediment layer. The sediment chemistry has been analyzed before and after the acidification by XRF. The water chemistry was sampled at time intervals and analyzed by ICP-MS. With a pH drop from 6.5 to 3.0, many elements increase in concentration in the water of the acidified basins. Enrichment factors were: Al (5000), Ba (10), Cd (220), Co (800), Cu (170), Ni (90), Pb (5000), and Zn (400). This corresponds fairly well with the field data. Al, Cd, Fe, Mn, and Pb exceed German drinking water limits at pH 4.0. The combined high concentrations (μg L^?1) of Al (1000–2600), Cd (2–4), Cu (4–7), Pb (30–60), and Zn (100–300) in the water column of the acidified streams are not only toxic for fish but also for many other aquatic organisms. Chemical changes in the sediment are not significant within the experimental setup.     

Sulfur constituents of sediments and their relationship to lake acidification

Sulfate is a major component of acid precipitation in the Northeastern United States. Transformations and fluxes of S may be important indices of the effect of acidification on limnetic systems. Sulfur constiuents and respiration rates were compared in sediments among Oneida, Deer and South Lakes in New York which exhibit a range of buffering capacity and pH from high to low, respectively. Total S in Deer and South was higher near their major inlets. Sulfide was highest in Oneida sediment, which had a lower redox potential (Eh). Ester sulfate was a major portion of the S in the three lakes. Oxygen consumption was highest in Oneida and lowest in South sediments. The low ester sulfate and an elevated C/N ratio of South sediment may indicate that acidification inhibits decomposition     

Effect of lake acidification on the adsorption of phosphorus by sediments

The retention properties of acidic and non-acidic lake sediments were determined in order to assess the effects of lake acidification on the immobilization of P from solution by sediments. The adsorption of P by solids was described by the Langmuir model which was used to determine the sorption parameters, e.g. sorption maxima and equilibrium constant of adsorption. The pH of solution and the chemical and mineralogical characteristics of sediments affect mainly the magnitude of adsorption maxima. The binding strength of the adsorbed complex is similar for all the investigated sediments (Δ=?25.3 to ?28.5 kJ mol^?1) and it is affected little by variation in pH or by chemical and mineralogical composition of sediments. The results indicate that the magnitude of P removal is determined more by sediment chemistry and mineralogy (amorphous Al/Fe oxy-hydroxides, carbonate content) than by pH of the water.     

Simulated mobilization of metals from sediments in response to lake acidification

The regeneratable forms of pollutant metals in lake sediments were estimated using different chemical extractants and the effects of lake acidification on the mobilization of such metal fractions studied in laboratory microcosm. The release of each metal was found to increase exponentially below a threshold pH value, which was about 4.0 for Cu, Ni, Zn, Cd and Fe. The data suggest that a large percentage of pollutant metals are mobile as determined by chemical extraction techniques and long-term release experiments.     

Influence of organic acids on model projections of lake acidification

We employed three mathematical models to make quantitative estimates of the pH of 33 statistically-selected lakes in the Adirondack mountains, New York (USA) prior to the Industrial Revolution (1840). The models included 1) the MAGIC watershed acidification model, 2) a paleolimnological model of diatom-inferred pH, and 3) the MAGIC model modified to incorporate an empirically-based model of natural organic acidity. Application of approaches 2) and 3) yielded consistent estimates of pre-industrial Adirondack lakewater pH. However, when the organic acid model was not included, MAGIC calculations and diatom-inferred values showed poor agreement. MAGIC projections of lakewater pH 50 years into the future, under differing atmospheric deposition scenarios, were also sensitive to inclusion of the organic acid model. MAGIC predicted greater recovery in response to reduced deposition when organic acids were not considered. These results suggest that failure to consider the pH buffering of naturally-occurring organic acidity will often result in biased projections which overemphasize the response of lakewater pH to changes in atmospheric inputs of strong acid.     

Detection of heavy metal pollution in estuarine sediments

Anomalies in the concentrations of heavy metals in estuarine sediments may not be reliably detected based on the measured concentration values or the ratios of metal concentrations to those of a reference element because of natural variations in both. However, the departure of a measurement from a regression line between metal and reference element concentrations may serve as a criterion for detecting an anomaly. The procedure has been applied to a suite of 34 sediments from a Florida estuary.     

Snowpack quality as an indicator of air pollution in Finnish Lapland and the Kola Peninsula,NW Russia

Bulk snow samples were collected from the snowpack in open areas along two sampling lines running to the west from the Cu-Ni smelters at Nikel and Monchegorsk, NW Russia, during 1991–1993. The aim of the study was to estimate the area affected by sulphur and heavy metal deposition from the smelters. Snowpack quality was used as an indicator of deposition during winter time. The total sulphur, copper and nickel concentrations in the snowpack decreased significantly (p<0.001) with=" increasing=" distance=" from=" the=" smelters=" along=" the=" sampling=" line=" running=" directly=" to=" the=" west=" from=" monchegorsk.=" the=" deposition=" pattern=" was=" similar=" each=" winter=" during=" 1991–1993.=" the=" ph=" values=" did=" not=" correlate=" with=" the=" corresponding=" sulphur=" concentrations,=" and=" there=" was=" no=" decreasing=" ph=" gradient=" in=" the=" snowpack=" on=" moving=" towards=" monchegorsk.=" the=" effects=" of=" sulphur=" emissions=" from=" monchegorsk=" on=" snowpack=" chemistry=" were=" not=" detectable=" on=" the=" finnish=" side=" of=" the=" border.=" the=" 3-year=" mean=" of=" the=" total=" sulphur=" concentration=" was=" 0.27=" mg/kg,=" and=" of=" the=" ph=" values=" 4.92,=" along=" the=" sampling=" line=" running=" to=" the=" west=" of=" monchegorsk.=" the=" total=" sulphur=" concentrations=" near=" the=" smelters=">< 20=" km)=" varied=" between=" 0.37=" and=" 0.95=" mg/kg.=" the=" effect=" of=" the=" cu-ni=" smelters=" at=" nikel=" on=" snowpack=" quality=" was=" not=" detectable=" in=" northern=" finnish=" lapland.=" the=" 3-year=" mean=" for=" total=" sulphur=" was=" 0.20=" mg/kg=" and=" for=" ph=" 4.96=" along=" the=" sampling=" line=" running=" to=" the=" west=" of=">     

Influence of incubation time on phosphorus sorption dynamics in lake sediments

Purpose  

Estimating phosphorus (P) sorption is generally achieved by measuring a decrease in P concentration over a defined period. However, information within the literature has not been able to be widely applied, probably due to the variability in incubation periods and initial P concentrations in reported experiments. The objective of this study was to investigate whether variations in incubation time and initial P concentration might result in differences in measured levels of P sorption in sediments.     

Biological indicators of lake acidification

Indicator taxa are identified, based on both synoptic surveys and whole lake acidification experiments, for lake acidification in the pH 6.0 to 5.0 range. Acidobiontic diatoms (e.g Asterionella ralfsii, Fragillaria acidobiontica, etc.), periphyton (Mougeotia and related species), macroinvertebrates (e.g. Hyalella azteca, Orconectes sp., etc.), leeches, and cyprinid fishes (e.g. Pimephales promelas, Notropis cornutus, etc.) are identified as target organisms during early phases of lake acidification.     

Chrysophyte scales in lake sediments provide evidence of recent acidification in two Quebec (Canada) lakes

Several lake surveys have indicated that many lakes in Quebec are sensitive to acidification, but no historical data are available to provide conclusive evidence of lake acidification. Paleolimnological studies can provide such evidence. Chrysophycean algal microfossils were analyzed from the sediments of Lake Bonneville and Lake Truite Rouge in Quebec. The chrysophyte flora in the study lakes was stable until 40 yr ago, but since then the taxa characteristic of acidic or slightly acidic waters increased in abundance. The study provides evidence of recent lake acidification in Quebec.     

Heavy metal pollution of agricultural soils and sediments in Liaoning Province,China

Heavy metal pollution of soils and sediments in Liaoning Province, Northeast China, was investigated. Fifty seven samples of agricultural soils and 8 samples of sediments were collected in 1996 from paddy or upland fields and irrigation channels, respectively, in Shenyang, Fushun, Liaoyang, Anshan, and Tieling regions, and concentrations of total and 0.1 mol L^-1 HCI-extractable Cd, Cu, Pb, and Zn were analyzed using ICP spectrometry. Seventeen samples of unpolished rice were also collected from selected paddy fields and total concentrations of the four elements were determined.–

Both paddy and upland soils were polluted with Cd: average total concentration was 0.70, 0.57, and 0.53 mg kg^-1 in the western and southern parts of Shenyang, and Anshan, respectively, and significantly higher than the background level of 0.32 mg kg^-1. Cd concentrations of four samples exceeded even 1 mg kg^-1, which corresponds to the critical level of Cd contamination in China. About 65% of the total Cd was extracted with 0.1 mol L^-1 HCI, suggesting that Cd was relatively mobile compared with other metals. The level of Cd pollution was, however, lower than that previously reported and serious polIution was not observed for Cu, Pb, and Zn. Accordingly, Cd concentration in upland rice was within the range of the unpolluted level in this study. Nevertheless, Cd concentration in a sediment of irrigation channels in the western part of Shenyang exceeded 16 mg kg^-1, indicating the possibility of further contamination of agricultural soils. In conclusion, soils and sediments were still polluted with Cd in the southern part of Shenyang, Anshan, and especially in the western part of Shenyang, and further countermeasures are urgently required to ensure safe food production in these regions.     

Regional monitoring of lake acidification in Finland

The primary objective of this monitoring is to detect long-term Long-Range Transboundary Air Pollution (LRTAP) induced changes in the water quality of small lakes, throughout Finland, with low conductivity. The monitored lakes (n=171, sampled every autumn since 1990 and in 1987) have a smaller watershed (usually headwater or seepage lakes), a larger lake/catchment ratio, and lower base cation concentrations, alkalinity and pH than Finnish lakes on average. The monitoring network provides background data for air pollution dose/response studies, critical load calculations and for the modelling of acidification scenarios. The declining sulphate deposition seems to be reflected in small headwater lakes all over southern and central Finland as a lowering of the sulphate concentration in the waters. Nitrate concentrations in these lakes have been typically low in the autumn. The base cation concentration is not generally declining, as it is in deposition in many areas. The sulphate concentration in lakes has declined more than base cations. Hydrologically, the recent years have been quite variable because of varying annual precipitation. The variation in alkalinity and pH in typical Finnish lakes is dependent on the content of humic material derived from catchments. The monitoring period is too short to reveal consistent trends in major ion chemistry. However, signs of improvement in recent years can be seen; in comparing 1993 to 1987, years with similar organic acidity and base cations, it seems that the sulphate decline in lakes monitored is compensated by a significant rise in both alkalinity and pH.     

Sulfur isotope fractionation and sequential extraction to assess metal contamination on lake and river sediments

Purpose

The present study investigated lake and river sediments affected by metals from an acid mine drainage (AMD) from a former uranium mine. The role of bacterial sulfate reduction in the immobilization of contaminants was evaluated, and the analyses of acid volatile sulfide (AVS) and sequential extraction were performed. Consequently, the potential mobility and bioavailability of contaminants were established.

Materials and methods

Sulfur isotopic fractionation (δ³⁴S), AVS, and sequential extraction procedure were used to assess the sulfate bacterial reduction and the availability of contaminants in the environment at six sampling stations.

Results and discussion

The δ³⁴S indicated that bacterial reduction is a key process in the natural attenuation of contamination in the Águas Claras reservoir, precipitating metal sulfides. According to the USEPA criteria, adverse biological effects are expected for sample S1 (inside the reservoir) which is likely to be toxic, while for sediment S4 (in the river), the toxicity is uncertain. The other samples were classified as non-toxic, likely because of the decreased solubility of zinc sulfide. A decrease in the concentration of the contaminants downstream of the reservoir was observed. The predominance of U (0.4 %) in the labile fraction and the elevated concentrations of Zn (0.5 %) and Mn (0.7 %) in the sediments inside the reservoir raises concerns regarding the availability of these contaminants in the environment.

Conclusions

The main environmental impact appears to be concentrated in the Águas Claras reservoir, whereas the Antas creek does not seem to be affected by the AMD process. Although the bacterial sulfate reduction is effective in its production of sulfides capable of immobilizing the contaminants, the presence of Zn and U in the labile and reducible fraction is a matter of concern due to its long-term bioavailability. Thus, continuous monitoring of the redox potential of the waters and sediments, mainly in the reservoir, is recommended in order to assess and possibly prevent later dissolution of sequestered contaminants.

     

Soil geochemistry in relation to water chemistry and sensitivity to acid deposition in Finnish Lapland

Ecosystems in Finnish Lapland are threatened by heavy metal pollution and acid deposition derived from emissions of Cu-Ni smelters in Kola Peninsula and to varying extent to pollution from southern Fennoscandian and Central European sources. Extensive chemical analyses of small lake waters collected in Finnish Lapland have demonstrated that a significant number of lakes are acidified (ANC < 0μcq/l) or their buffering capacity is critical (ANC = 0–50μe/l). The relative abundance of mafic, ultramafic and carbonate rock components in the catchment were the chief factors controlling ANC and the main base cation (Ca²⁺, Mg²⁺) concentrations of lake waters. Both humic and clearwater lakes with low buffering capacity (ANC < 50μeq/l) were mainly located in the catchment areas identified as sensitive to acidification on the basis of low content of base cations (Ca²⁺ +Mg²⁺ +K⁺ < 500 meq/kg) in till. The ratio of the catchment area to the lake area was distinctly smaller for acidic lakes than for the well-buffered lakes, indicating the importance of catchment processes in determining the ANC and main base cations. The high sulphur concentrations (median 60μeq/1) of acidic lakes in northeastern Lapland, near the Finnish-Norwegian border, were strongly correlated with the highest deposition of sulphur derived from smelters of Kola Peninsula. The anomalously high concentrations of sulphur of well-buffered lakes in the western part of Lapland were due to sulphide minerals of soil and bedrock. The acidity of humic lakes in southern Lapland was in large part due to the organic acidity derived from peatlands.     

Soil acidification by atmospheric pollution and forest growth

In recent years concern has been expressed about the danger of harmful pollution deposits which affect areas at great distances from the emission sources. The investigation was so designed that a possible reaction in growth resulting from a supposed acidification could be observed as far as possible. A poorer growth development was observed in regions, which are suspected of being more susceptible to acidification than those regions which are presumed to be less susceptible in this respect. We have found no good reason for attributing the reduction in growth to any cause other than acidification.     

Effect of submerged macrophytes on metal and metalloid concentrations in sediments and water of the Yunnan Plateau lakes in China

Purpose

Submerged macrophytes have an ability to absorb metals and metalloids either from the sediments via the roots, from the water by the leaves, or from both sources. The objectives of this study were (1) to test the hypothesis that metal and metalloid concentrations in water and sediments from sampling sites with submerged macrophytes are significantly lower than those from sampling sites without submerged macrophytes, (2) to explore the accumulation potential for metals and metalloids of different submerged macrophyte species, and (3) to discuss the relationships among submerged macrophytes, water, and sediments in the Yunnan Plateau lakes.

Materials and methods

Twenty Yunnan Plateau lakes with different trophic levels were selected. Concentrations of 16 metals and metalloids (Al, As, Ba, Cd, Co, Cr, Cu, Fe, Li, Mn, Mo, Ni, Pb, Se, Sr, and Zn) in submerged macrophytes, water, and sediments were determined by using ICP-AES. Relationships among metal and metalloid concentrations in water, sediments, and submerged macrophytes were carried out by Pearson correlation analysis. The enrichment factor was calculated as the ratio between the concentration of metals and metalloids in a sediment sample and the soil background value.

Results and discussion

No significant differences were found in metal and metalloid concentrations in water and sediments between sampling sites with submerged macrophytes and sampling sites without submerged macrophytes. Moreover, lake water and sediments were mainly contaminated by As, Cr, and Pb. Potamogeton distinctus is a hyperaccumulator of Fe according to the threshold value for Fe hyperaccumulation. Many significantly positive correlations were found among metals and metalloids in submerged macrophytes due to co-accumulation. We found significant correlation between Cr in submerged macrophytes and Cr in water, and strong positive correlations between As, Cd, and Cu in submerged macrophytes and As, Cd, and Cu in corresponding sediments in the Yunnan Plateau lakes.

Conclusions

Submerged macrophytes have no significant effects on metal and metalloid concentrations in sediments and water in all the 20 Yunnan Plateau lakes in the study. However, further studies are necessary to understand the interactions of metals and metalloids in submerged macrophytes, water, and sediments.

     

recent lake acidification and recovery trends in southern quebec,canada

A total of 51 lakes in southern Quebec, Canada, were sampled between 1985 and 1993 to study changes in water chemistry following reductions in SO₂ emissions (main precursor of acid precipitation). Time series analysis of precipitation chemistry revealed significant reductions in concentrations and deposition of SO₄ ^2- from 1981 to 1992 in southern Quebec as well as reductions in concentrations and deposition of base cations (Ca²⁺, Mg²⁺), NO₃ ^- and H⁺ in the western section of the study area. Reductions in atmospheric inputs of SO₄ ^2- have resulted in decreased lakewater SO₄ ^2- concentrations in the majority of the lakes in our study, although only a small fraction (9 of 37 lakes used in the temporal analysis) have improved significantly in terms of acidity status (pH, acid neutralizing capacity – ANC). The main response of the lakes to decreased SO₄ ^2- is a decrease in base cations (Ca²⁺+Mg²⁺), which was observed in 17 of 37 lakes. Seventeen lakes also showed significant increases in dissolved organic carbon (DOC) over the period of study. The resulting increases in organic acidity as well as the decrease in base cations could both play a role in delaying the recovery of our lakes.