Organic Matter Diagenesis in Acidic Mine Lakes

The significance of organic matter origin for carbon oxidation via sulfate and iron reduction in the sediments of three acid mine lakes is analyzed. Carbon reactivity was estimated by fitting first‐order expressions to measured rates. Carbon oxidation rates via sulfate and ferric iron reduction ranged from 3.4 to 4.7 mmol m^–2 d^–1 and resembled those reported for freshwater lakes. The estimated reaction constants increased from about 10^–3 a^–1 at the interface to the former mine grounds to 0.05 to 0.2 a^–1 at the current sediment‐water interface. Aquatic organic matter accounted for an estimated 45...75% of total carbon oxidation rates while it amounted only to about 5...14% of the total organic matter that had been deposited. The results of this study suggest that in highly acidic mine lakes the reactivity of the deposited organic matter can rapidly increase after flooding, enhancing carbon oxidation and internal neutralization rates in the sediments.     

Verringerung der Schwermetall‐ und Sulfatbelastung in sauren bergbaubelasteten Gewässern durch Aluminiumpräzipitate

Attenuation of Heavy Metals and Sulfate by Aluminium Precipitates in Acid Mine Drainage During the mixing of acid mine waters with nearly neutral tributaries, often precipitates are formed which are high in iron or aluminium. These precipitates cover the river bed for many kilometres. Near the town of Lehesten (Thuringian slate mining area), leachates of slate quarries and waste rock dumps contain high amounts of aluminium, sulfate, copper, nickel, zinc, manganese, and H⁺ ions as a result of the oxidation of incorporated pyrite. These leachates enter the brooks Loquitz, Kleine Sormitz, and Rehbach leading to the phenomenon named above. The contribution of the forming aluminium‐rich precipitates on the attenuation of sulfate and heavy metals by sorption or coprecipitation was studied by analysing the composition of water and sediment samples as well as samples of suspended matter. Sulfate is often considered as conservative tracer in acid mine drainage. However, sulfate does not behave conservatively in this system what might be explained by the adsorption of sulfate to the aluminium precipitates. Instead, conservative behaviour was found for calcium, potassium, chloride, zinc, manganese, and nickel. A formation of jurbanite can be excluded because of the low sulfate contents. The sulfate content of the sediment depends on the pH. At low pH values (4.8) the S/Al ratio corresponds to the theoretical ratio in basaluminite and decreases with rising pH. Sulfate is weakly bound to the solid phase and can easily be replaced by OH^– ions. A formation of basaluminite is possible at low pH values with a fluent transition to aluminium hydroxide. Therefore the precipitates are assumed to consist predominantly of aluminium hydroxide with sulfate being adsorbed to the surface.     

Scaling and correlation of atmospheric acid deposition evolutions

Detrended fluctuation analysis (DFA) and power spectrum density are applied to verify the presence of temporal scaling behavior and long-range persistence (LRP) of weekly hydrogen ion deposition (WHD), NO₃^- and SO₄^2- deposition series in National Atmospheric Deposition Program, USA, for the period 1978–2001. The results show a common scaling behavior for all sites analyzed. Two distinct scaling regions are identified by DFA1, one corresponding to 1 month to 1 year and the other to 1 year to 5 years. The WHD series obey power-law in two temporal regimes respectively with mean DFA1 scaling exponents α ₁≈0.68 and α ₂≈0.45, implying the presence of LRP in the acid deposition series and there is a tendency for a large deposition event to be followed by another large event, and vice versa. For DFA2–DFA4, however, the annual crossover, which divides the temporal scale into two regimes, disappears gradually with the order q of DFAq increasing, and the two scaling regimes turn to share the same scaling exponent close to α ₁. The result indicates that the scaling behavior exits in the two regimes with the same scaling exponent α ₁, and LRP prevails during the examined 1-month to 5-years scale. NO₃^- and SO₄^2- deposition evolve the same way as WHD does, implying the pollutants involving in acid deposition may share some prominent mechanism controlling their evolutions. We ascribe the long-range power-law scaling of acid deposition evolutions to the self-organized critical behavior of atmosphere under pollution stress and it should be considered in the trend prediction of acid deposition as an important factor.     

Incorporation of Heavy Metals Bioavailability into Risk Characterization

The bioavailability of field‐aged Cd and Cu was calculated, and compared to the total concentrations determined by acid digestion. Only 0.60–4.15% for Cd and 0.59–9.43% for Cu were found to be bioavailable when determined by stomach‐phase extraction. The incorporation of bioavailability reduced more than 90% of the calculated risk of the metals at the site of study. It should be noted that such a reduction may not be generalized and the site‐specific bioavailability needs to be determined case by case.     

Patterns of dissolved organic matter in subarctic peatlands

Samples of water from poor to very rich fens in the Schefferville region of subarctic Quebec revealed strong spatial and temporal variations in dissolved organic carbon (DOC), ranging from 2 to 40 mg 1^?1. Concentrations of DOC tend to increase during the summer and decrease in the autumn, at most sites, which probably reflects increased plant tissue decomposition and higher rates of evapotranspiration. Principal components analysis revealed that DOC is strongly associated with Fe, NO^?₃-N and NO^?₂-N, but essentially independent of other chemical properties of the peat water, such as pH, Ca, Mg, K, P, and NH⁺₄-N. Based on observed concentrations of DOC and estimates of summer runoff (June to September), export of DOC from four peatlands ranges from 1·1 to 4·9 gCm^?2, with the lowest values for peatlands underlain by dolomite. Molecular weight fractionation of four samples revealed significant differences in the dissolved organic matter (DOM), with the largest fractions (GF/C to 10 000 nmw) being dominant in the more acid samples. The ratio of absorbance at 400 and 600 nm wavelengths (E₄:E₆) has been used as a simple indicator of differences in DOM type, ranging from 3 to 15. There is a strong seasonal pattern of increasing E₄:E₆ ratio during the summer at many sites, though this ratio is essentially independent of other chemical properties of peat waters.     

Downstream patterns of bed sediment-borne metals,minerals and organic matter in a stream system receiving acidic mine effluent: A preliminary study

Different downstream variation patterns were observed for a range of bed sediment-borne metals (aqua regia-extractable fraction) in a subtropical stream system receiving acid mine drainage. Mine-originated Fe tended to be deposited in the acidic (mean pH < 4.9) upstream reach in forms of goethite and/or hematite. In contrast, other metals tended to be transported farther downstream and settled in a low-gradient reach with high pH (mean pH > 5.6). The peak of sediment-borne Al, Be, Ca, Cd, Co, Cu, La, Mn, Ni and Zn corresponded very well with the peak of the sediment-borne organic matter, suggesting a close association between the water-borne organic colloids and the inorganic metal oxides/hydroxides during their transport. The marked increase in the sediment-borne Al and Pb started more upstream than the other metals, suggesting that the water-borne Al and Pb were more susceptible to pH rise-induced precipitation, as compared to the other metals. It appeared that the organic colloids played no important role in Pb transport and settlement. The iron precipitates had a limited role to play in affecting the transport and fates of other metals since they were predominantly formed and deposited in the acidic reach, which made them incapable of scavenging cationic metals by co-precipitation or adsorption.     

无锡梅雨期湿沉降综合分析

利用2008—2014年梅雨期间酸雨观测资料及2014年6月16—27日降水个例加密采样资料,结合大气污染物资料分析了近7 a无锡梅雨期酸雨特征,研究降水过程中空气污染物、p H值、电导率的变化及降水对污染物的清除作用。结果表明:无锡市梅雨期酸雨年平均p H值呈现逐年递增趋势。降水过程中,颗粒物质量浓度显著降低;气体浓度变化受其自身日变化及排放源影响大于雨水的清除作用;样品的p H值、K值每个过程变化并不一致,K值变化与颗粒物质量浓度变化大致保持一致。降水、风对颗粒物质量浓度影响大于对气体浓度的影响。长时间连续降水时,降水对颗粒污染物的清除存在极限。小时雨量在0~0.5 mm时,降水对颗粒物浓度做负清除,其值反而略有增加;小时雨量在0.6~5.0 mm时,降水对颗粒物质量浓度做正清除;小时雨量达到5.1 mm及以上时,对PM_(2.5)和PM_(2.5-10)做正清除,对PM_(10)做负清除。降水对SO_2有稀释清除作用;对NO_2的稀释作用取决于其开始浓度值;对CO、O_3的清除作用不显著。     

A mass balance approach to estimate the dilution and removal of the pollutants in stream water polluted by acid mine drainage

 A few simple mass balance equations were developed to simultaneously estimate how much the pollutants from acid mine drainage (AMD) in stream water are diluted and removed during their migration. The application of the equations requires knowledge of the variations in the concentrations of the dissolved pollutants and the stoichiometry of the precipitation reaction of the pollutants when none of the pollutant shows a conservative behavior along the stream path. The calculation should be restricted to the pollutants showing much higher concentrations in the polluted main stream water than in the combining or diluting water of the same target area. The mass balance equations were applied to estimate the dilution factor and precipitation fractions of pollutants in Imgok Creek such as Fe, SO₄ and Al from the AMD of Yeongdong mine. The results show that the estimation, especially for SO₄ and Al, significantly depends on the kinds of the precipitates. When FeOHSO₄ and AlOHSO₄ are assumed to precipitate, the maximum removal fractions of SO₄ and Al by precipitation are respectively 34% and 46% of the original input, which is much higher than the values estimated when SO₄ is considered to be perfectly conservative. It indicates that the stoichiometry of precipitation reaction is very important in the interpretation of the pollutant dilution and migration and assessment of environmental impacts of AMD. The applicability of the mass balance equations may still need to be verified. However, examining the calculated dilution factor and precipitation fractions with the equations can provide invaluable information on not only the behavior but also unexpected input of the pollutants in the stream water polluted by AMD and other point sources. Received: 12 November 1997 · Accepted: 30 March 1998