Environmental assessment of copper–gold–mercury mining in the Andacollo and Punitaqui districts,northern Chile

The Coquimbo region has been one of the richest producers of Cu, Au and Hg in Chile, and some of the deposits have been mined almost continuously since the 16th century. To assess the potential environmental contamination in this region, the authors measured the concentration of Cu, As, Cd, Zn and Hg in samples of stream and mine waters, stream sediments, soils, flotation tailings, and mine wastes in the Andacollo (Cu, Au, Hg) and Punitaqui (Cu–Au, Hg) districts. The concentration of Hg in the atmosphere in these districts were also measured. Although contamination is strongly controlled by the ore in each district, metal dispersion is modified by the degree of metallurgical processing efficiency as shown by the outdated Cu flotation system at Andacollo (stream sediments Cu 75–2200 μg/g). Conversely, more efficient procedures at Punitaqui resulted in less stream contamination, where stream sediments contained Cu ranging from 110–260 μg/g. However, efficient concentration by flotation of a given metal (e.g. Cu) may lead to the loss of another (e.g. Hg up to 190 μg/g in the tailings at Punitaqui), and therefore, to contamination via erosion of the tailings (downstream sediments Hg concentrations up to 5.3 μg/g). Continued use of Hg for Au amalgamation at Andacollo has led to significant contamination in stream sediments (0.2–3.8 μg/g Hg) and soils (2.4–47 μg/g Hg). Communities in this region are underdeveloped, and decades of inefficient treatment of flotation tailings and waste-rock stock piles has resulted in significant contamination of the surrounding landscape.     

Regional geochemical baseline concentration of potentially toxic trace metals in the mineralized Lom Basin,East Cameroon: a tool for contamination assessment

The distribution of trace metals in active stream sediments from the mineralized Lom Basin has been evaluated. Fifty-five bottom sediments were collected and the mineralogical composition of six pulverized samples determined by XRD. The fine fraction (<?150 µm) was subjected to total digestion (HClO₄?+?HF?+?HCl) and analyzed for trace metals using a combination of ICP-MS and AAS analytical methods. Results show that the mineralogy of stream sediments is dominated by quartz (39–86%), phyllosilicates (0–45%) and feldspars (0–27%). Mean concentrations of the analyzed metals are low (e.g. As?=?99.40 µg/kg, Zn?=?573.24 µg/kg, V?=?963.14 µg/kg and Cr?=?763.93 µg/kg). Iron and Mn have significant average concentrations of 28.325 and 442 mg/kg, respectively. Background and threshold values of the trace metals were computed statistically to determine geochemical anomalies of geologic or anthropogenic origin, particularly mining activity. Factor analysis, applied on normalized data, identified three associations: Ni–Cr–V–Co–As–Se–pH, Cu–Zn–Hg–Pb–Cd–Sc and Fe–Mn. The first association is controlled by source geology and the neutral pH, the second by sulphide mineralization and the last by chemical weathering of ferromagnesian minerals. Spatial analysis reveals similar distribution trends for Co–Cr–V–Ni and Cu–Zn–Pb–Sc reflecting the lithology and sulphide mineralization in the basin. Relatively high levels of As were concordant with reported gold occurrences in the area while Fe and Mn distribution are consistent with their source from the Fe-bearing metamorphic rocks. These findings provide baseline geochemical values for common and parallel geological domains in the eastern region of Cameroon. Although this study shows that the stream sediments are not polluted, the evaluation of metal composition in environmental samples from abandoned and active mine sites for comparison and environmental health risk assessment is highly recommended.     

Distribution of heavy metals in the clastic fine-grained sediments of Gavkhuni playa lake (Southeast of Isfahan,Iran)

The sedimentary basin of Gavkhuni playa lake includes two sedimentary environments of delta and playa lake. These environments consist of mud, sand and salt flats. There are potentials for concentration of heavy metals in the fine-grained sediments (silt and clay) of the playa due to existence of Pb/Zn ore deposits, industrial and agricultural regions in the water catchment of Zayandehrud River terminating to this area. In order to study the concentration of heavy metals and the controlling factors on their distribution in the fine-grained sediments, 13 samples were taken from the muddy facies and concentration of the heavy metals were determined. The results showed that the heavy metal concentrations range in the sediments (in ppm) are Mn (395.5–1,040), Sr (100.4–725.76), Pb (14.66–91.06), Zn (23.59–80.9), Ni (37–73.66), Cu (13.83–29.83), Co (5.73–13.78), Ag (3.03–4.76) and Cd (2.3–5.5) in their order of abundances. The concentration of Ag is noticeable in the sediments relative to the average concentration of this element in mud sediments. The amounts of Pb and Zn are relatively high in all the samples in comparison with the other elements. The concentration of Ni is relatively high in the oxidized samples. The distribution of Pb is directly related to organic matter content of the sediments. The concentrations of Zn, Sr, Cu, Co and Cd in the samples of the playa are lower than those in the delta. The amount of illite is another factor influencing Zn and Pb concentrations. Sr is more concentrated in the sediments with the high content of calcium carbonate. The distribution pattern of Cu, Co, Pb and Mn resembles to that of the clay content of the sediments. The clay content shows positive correlations with Co, Cu and Mn concentrations and negative correlation with Ag. The Sr and Ag concentrations are positively correlated with the amount of CaCO₃. The amounts of Co, Cu, Ni and Mn show negative correlations with the calcium carbonate content. Pb and Co are noticeably correlated with Mn.     

Mercury pollution as a result of gold extraction in North Carolina,U.S.A.

Water, sediment and panned concentrate from active streams, together with some mosses and well waters, all from the vicinity of old Au operations in North Carolina, were analyzed to determine the extent of pollution from metallic Hg introduced into these areas in the 1800s and early 1900s and by modern “weekend panners”.Heavy mineral concentrates, Au grains, sediment and moss were all found to be indicators of Hg pollution, with concentrations of up to 784,000 μg/kg in heavy mineral concentrates, 7400 μg/kg in sediments, and 4900 μg/kg in moss. Surficial spots on Au grains contained as much as 44.8% Hg. Analyses of fish tissue from several of the drainage channels did not indicate Hg pollution with all values below the North Carolina average of 210 μg/kg. Mercury concentrations in stream and well waters were all below the LLD of 0.2 μg/l. In North Carolina, heavy mineral concentrates appear to be the best indicators of introduced metallic Hg.     

Partitioning of copper and zinc in the sediments and porewaters of a high-elevation alkaline lake,east-central Arizona,U.S.A.

In Pacheta Lake, a high-elevation alkaline lake proximal to the smelting region of southern Arizona-New Mexico, concentrations of transition metal ions in pore waters and co-existing sediments were compared. Copper, Fe, Mn and Zn have been partitioned among operationally defined sediment solid phases (exchangeable sites, organic complexes, amorphous oxides, crystalline oxides, sulfides and residual silicates) and their concentrations in interstitial waters were measured. Concentrations are reported as a function of depth in the sediment column. The diagenetic environment is described and cycling mechanisms postulated for the above metals.Selective, sequential extraction of metals from lake sediments showed different binding mechanisms for Cu and Zn, the former most strongly associated with organic complexes, and the latter with iron oxyhydroxides. This difference has strong implications for selective metal remobilization under variable environmental conditions, both naturally and anthropogenically induced. Copper and zinc in porewaters were estimated to diffuse to overlying waters at 12.8 and 21.9 μg/cm²/a, respectively. These fluxes are large enough to account for observed concentrations of Cu and Zn in overlying waters. No sediment metal contamination was directly attributable to smelting activity. However, this study does document a flux from sediments, which have accumulated Cu and Zn, to overlying waters no longer receiving trace metal deposition from now inactive smelters.     

Concentrations and solubility of heavy metals in muck sediments from the St. Lucie Estuary,U.S.A.

To evaluate muck sediments as a potential soil amendment, total and Mehlich III-extractable concentrations of Cd, Cu, Cr, Ni, Pb, Zn, and Co in 59 muck sediment samples from the St. Lucie Estuary were analyzed. A seven-step chemical fractionation procedure was used to assess the potential mobility of heavy metals. Except for Cd, the average total concentrations of the metals are lower than the reported average concentrations of these elements in municipal composts in the U.S.A. The concentrations were also below critical levels for the safe use of wastes and byproducts in agriculture, as established by the United States Environmental Protection Agency. The Cd, Cu, Cr, Ni, Pb, Zn and Co in the sediments were predominantly associated with silicate minerals in the residual form. Most metals in the muck sediments occur predominantly in weakly mobile or nonbioavailable forms. Use of mucks in neutral pH upland soils should not pose any significant hazards or risk to the environment. However, Cd, Cu, Cr, Ni, Pb, Zn, and Co, especially Zn, Cu, and Pb, could be more readily released from the muck sediments under acidic soil conditions.     

Distribution of Cu,Co, As,and Fe in mine waste,sediment, soil,and water in and around mineral deposits and mines of the Idaho Cobalt Belt,USA

The distribution of Cu, Co, As and Fe was studied downstream from mines and deposits in the Idaho Cobalt Belt (ICB), the largest Co resource in the USA. To evaluate potential contamination in ecosystems in the ICB, mine waste, stream sediment, soil, and water were collected and analyzed for Cu, Co, As and Fe in this area. Concentrations of Cu in mine waste and stream sediment collected proximal to mines in the ICB ranged from 390 to 19,000 μg/g, exceeding the USEPA target clean-up level and the probable effect concentration (PEC) for Cu of 149 μg/g in sediment; PEC is the concentration above which harmful effects are likely in sediment dwelling organisms. In addition concentrations of Cu in mine runoff and stream water collected proximal to mines were highly elevated in the ICB and exceeded the USEPA chronic criterion for aquatic organisms of 6.3 μg/L (at a water hardness of 50 mg/L) and an LC50 concentration for rainbow trout of 14 μg/L for Cu in water. Concentrations of Co in mine waste and stream sediment collected proximal to mines varied from 14 to 7400 μg/g and were highly elevated above regional background concentrations, and generally exceeded the USEPA target clean-up level of 80 μg/g for Co in sediment. Concentrations of Co in water were as high as in 75,000 μg/L in the ICB, exceeding an LC50 of 346 μg/L for rainbow trout for Co in water by as much as two orders of magnitude, likely indicating an adverse effect on trout. Mine waste and stream sediment collected in the ICB also contained highly elevated As concentrations that varied from 26 to 17,000 μg/g, most of which exceeded the PEC of 33 μg/g and the USEPA target clean-up level of 35 μg/g for As in sediment. Conversely, most water samples had As concentrations that were below the 150 μg/L chronic criterion for protection of aquatic organisms and the USEPA target clean-up level of 14 μg/L. There is abundant Fe oxide in streams in the ICB and several samples of mine runoff and stream water exceeded the chronic criterion for protection of aquatic organisms of 1000 μg/L for Fe. There has been extensive remediation of mined areas in the ICB, but because some mine waste remaining in the area contains highly elevated Cu, Co, As and Fe, inhalation or ingestion of mine waste particulates may lead to human exposure to these elements.     

Spatio-temporal trends of heavy metals and source apportionment in Tolo Harbour,Hong Kong

This study provided a picture of the spatial and temporal distributions of Cr, Co, Ni Cu, Zn, As, Cd and Pb in bottom sediments of Tolo Harbour. The concentrations of the eight heavy metals differed significantly between sites due to the poor tidal flushing in Tolo Harbour. The levels of Cu, Zn, Cd and Pb were generally enriched in sediments from inner Tolo Harbour, while sediments from outer Tolo Harbour (Tolo Channel) had higher levels of Cr, Co and Ni. The redox sensitive element arsenic showed no distinct spatial pattern in Tolo Harbour. The decreasing levels of Cu, Zn, Pb and Cd in sediments with increasing distance from land demonstrated a typical diffusion pattern from land to the direction of sea. Two hot spots of Cu, Zn, Pb and Cd in sediments were located near Tai Po and Sha Tin new town, indicating that Cu, Zn, Pb and Zn were from land-derived sources. The sites with relatively high levels of Cr, Co and Ni in sediments were located in areas close to waste spoil in sea floor. The natural and anthropogenic inputs from Sha Tin and Tai Po to Tolo Harbour were mostly responsible for Cu, Zn, Cd and Pb enrichment in sediments from inner Tolo Harbour. The waste spoil in sea floor was believed to contribute to the Cr, Co and Ni in outer Tolo Harbour. The results of correlation coefficient between the eight heavy metals showed that Cu, Zn, Cd and Pb were strongly positively correlated, and Cr, Co and Ni were also significantly correlated with each other. The best explanation of strong correlation was their similar source. As, however, is not well correlated with the other seven heavy metals. The average concentrations of Cu and Zn displayed general increasing trends from 1978 to 2006 in Tolo Harbour, while the mean levels of Cr and Pb displayed a substantial decrease from 1978 to 1987, then a slight increase after 1987. No distinct temporal trends of the concentrations of Ni and As were observed from 1978 due to the inconsecutive data. On the other hand, the increasing trends of Cr, Cu, Zn, Cd and Pb were observed since 1996.     

Tidal river sediments in the Washington,D.C. area. I. Distribution and sources of trace metals

Thirty-three bottom sediments were collected from the Potomac and Anacostia rivers, Tidal Basin, and Washington Ship Channel in June 1991 to define the extent of trace metal contamination and to elucidate source areas of sediment contaminants. In addition, twenty-three sediment samples were collected directly in front of and within major storm and combined sewers that discharge directly to these areas. Trace metals (e.g., Cu, Cr, Cd, Hg, Pb, and Zn) exhibited a wide range in values throughout the study area. Sediment concentrations of Pb ranged from 32.0 μg Pb g^?1 to 3,630 μg Pb g^?1, Cd from 0.24 μg Cd g^?1 to 4.1 μg Cd g^?1, and Hg from 0.13 μg Hg g^?1 to 9.2 μg Hg g^?1, with generally higher concentrations in either outfall or sewer sediments compared to river bottom-sediments. In the Anacostia River, concentration differences among sewer, outfall, and river sediments, along with downriver spatial trends in trace metals suggest that numerous storm and combined swers are major sources of trace metals. Similar results were observed in both the Tidal Basin and Washington Ship Channel. Cadminum and Pb concentrations are higher in specific sewers and outfalls, whereas the distribution of other metals suggests a more diffuse source to the rivers and basins of the area. Cadmium and Pb also exhibited the greatest enrichment throughout the study area, with peak values located in the Anacostia River, near the Washington Navy Yard. Enrichment factors decrease in the order: Cd>Pb>Zn>Hg>Cu>Cr. Between 70% and 96% of sediment-bound Pb and Cd was released from a N₂-purged IN HCl leach. On average, ≤40% of total sedimentary Cu was liberated, possibly due to the partial attack of organic components of the sediment. Sediments of the tidal freshwater portion of the Potomac estuary reflect a moderate to highly components area with substantial enrichments of sedimentary Pb, Cd, and Zn. The sediment phase that contains these metals indicates the potential mobility of the sediment-bound metals if they are reworked during either storm events or dredging.     

Geochemical indicators of gold-rich zones in the La Josefina epithermal deposit,Deseado Massif,Argentina

The gold deposit at La Josefina, in the Deseado Massif of Argentina, is a low-sulfidation epithermal deposit with some features of the intermediate sulfidation style; the Au occurs in quartz veins and hydrothermal breccias hosted by acid pyroclastic rocks produced by Jurassic bimodal volcanism. Exploration for this deposit type uses geochemical data for vectoring to mineralized rocks. Although a general suite of elements with anomalous concentrations around low-sulfidation deposits is known, that suite varies amongst individual deposits, which should be studied individually. The aim of this study was to determine, in the La Josefina deposit, geochemical indicators of Au-rich rocks at different scales and to assess the effects of weathering on those indicators. To reach these objectives, a mineralized zone (hosting Au-rich veins) and a non-mineralized zone (hosting barren veins) were compared in terms of vein mineralogy, alteration minerals and geochemistry. These zones were also compared with estimated element concentrations of the protolith. Element concentrations in the mineralized zone were then plotted against distance to the Au-rich veins, separating the dataset into two subsets: one from strongly oxidized rocks and the other from weakly oxidized rocks, considering the degree of oxidation as indicative of relative degree of weathering. Based on alteration and vein mineralogy, we interpret that the mineralized zone was hydrothermally active before, during and after Au-mineralization, while the non-mineralized zone was active only before Au-mineralization. Therefore, differences in element concentrations between the estimated protolith and the non-mineralized zone represent geochemical changes produced before mineralization, whereas differences between mineralized and non-mineralized zones represent changes produced during and after mineralization. We conclude that in rhyolitic to rhyodacitic pyroclastic rocks of the study area, affected by predominantly argillic and silicic hydrothermal alterations, high concentrations of Au, Cu, Hg, V, Co and P, and low concentrations of Ba are probably the best deposit-scale geochemical indicators to distinguish Au-mineralized zones from non-mineralized zones. High concentrations of As, Mn, Fe, Pb, Cr, Ni, MgO and Zn (as well as high values of chlorite-carbonate-pyrite index), and low concentrations of Be and CaO can also distinguish mineralized from non-mineralized zones. High concentrations of Au, Cu, Pb, As, Hg, and Co indicate Au-rich zones, independently of lithology and alteration, because they were introduced into the veins and host rocks together with Au. At detailed-scale, the concentrations of 15 elements vary with distance to Au-rich veins; therefore, those elements are considered potential indicators of proximity to Au-rich veins. Of those elements, Au, P, Cu, Pb, Hg, Ba and MgO are the strongest indicators of proximity to the Au-rich veins. In strongly oxidized rocks, some indicators of mineralized zones (Co, Mn, Pb, Zn and MgO) and some indicators of proximity to Au-rich veins (P, Au, Cu, Hg and Ba) should be used with caution or be avoided because weathering modifies their quality as indicators.     

Partitioning of manganese,iron, copper,zinc, lead,cobalt, and nickel in black coatings on stream boulders in the vicinity of the Magruder mine,Lincoln Co., Georgia

Sequential digestions of Fe-Mn oxide coated boulders collected upstream and downstream from the Magruder mine, Lincoln Co., Georgia, indicate probable partitioning relationships for Zn, Cu, Pb, Co, and Ni with respect to Mn and Fe. Initial digestion with 0.1M hydroxylamine hydrochloride (Hxl) in 0.01M HNO₃ selectively dissolyes Mn oxides, whereas subsequent digestion with 1:4 HCl dissolves remaining Fe oxides.The results indicate that partitioning is not constant, but varies systematically with respect to the location of metal-rich waters derived from sulfide mineralization. Upstream from the mineralized zone Zn and Ni are distinctly partitioned to the Fe oxide component and Co and Cu are partitioned to the Mn oxide component. Immediately downstream from the mineralized zone, Mn oxides become relatively more enriched in Zn, whereas Fe oxides are relatively more enriched in Cu, Co, and Ni. Analytical precision for Pb is poor, but available data suggests it is more closely associated with Fe oxides.For routine geochemical surveys utilizing coated surfaces, a one-step digestion method is probably adequate. Parameters useful for detecting sulfide mineralization are metal concentrations normalized to surface area or various ratios (e.g. Zn/(Mn + Fe), Cu/Mn, Pb/Fe). Ratios can be obtained much faster, and at lower analytical costs than conventional analysis of stream sediment.     

Hydrocarbons in the water and bottom sediments of a region with continuous petroleum contamination

The abundances and compositions of aliphatic hydrocarbons (AHC) and polyaromatic hydrocarbons (PAH) were investigated in the water and bottom sediments of the southwestern Amur Bay in the Sea of Japan. The water contained from 0 to 129 μg/1AHC (averaging 42.2 μg/l) and from 5 to 85 ng/l PAH (averaging 18 ng/l). The bottom sediments contained 168–2098 μg/g AHC and 7.2–1100 ng/g dry mass PAH. It was shown that the input of anthropogenic HC is better recorded by molecular markers than the distribution of AHC and PAH concentrations. The discovery of elevated HC concentrations in the bottom water layer suggests that the bottom sediments induced secondary contamination of the water body.     

砂岩铀矿成矿过程与氧化还原分带: 铀系不平衡证据

铀系不平衡技术被用来研究新疆伊犁盆地库捷尔太砂岩型铀矿床的氧化还原分带和成矿过程.取自该矿床的26个样品的铀、钍含量以及234 U/ 238U, 230 Th/ 234 U和230 Th/ 238U活度比值分别用ICP -MS和α能谱仪进行了测量.不同氧化还原带岩石的铀、钍含量和钍/铀比明显不同: 强氧化带岩石的U、Th含量和Th/U比分别为12.4 μg/g, 4.5 μg/g和0.48; 弱氧化带分别为20.4 μg/g, 5.0 μg/g和0.38; 过渡带(矿化带)分别为169.7μg/g, 4.7μg/g和0.07; 还原带(未蚀变带)分别为6.8μg/g, 3.7μg/g和0.87.其同位素特征亦有明显差异: 氧化带岩石234 U/ 238U大多大于1, 过渡带(矿化带)岩石部分大于或等于1, 部分小于1, 还原带(未蚀变带)岩石大多大于1; 氧化带岩石230 Th/ 234 U和230 Th/ 238U大多大于1, 过渡带(矿化带)岩石大多小于或等于1, 还原带(未蚀变带)岩石大多大于1.这可作为砂岩型铀矿床矿体定位的指示剂.铀系不平衡特征还示踪了该矿床的成矿作用过程.      

Carbonates — a guide to hydrocarbons

Unfrozen samples of pure water and 10% v/v nitric acid, stored in acid-cleaned linear (high-density) polyethylene containers, are used as contamination blank controls for hydrogeochemical samples preserved by deep-freezing in similar vessels. After four years the maximum levels of metal contaminants in these blanks are (in μg/1) Fc 0.4; Cr 0.6; Ni 1.0; TI 0.6; Co 1.5; Mn 0.14; Ag 0.17; Cu 1.5; Cd 0.17; Pb 2.4; Zn 2.4. Values slightly lower than these are found for Co, Mn, Ag, Cu, Zn and Pb in the pure water samples. Approximately 0.5–1.0 μg/l of both Zn and Pb are derived from the nitric acid.     

Geochemistry and morphology of metalliferous sediments and oxyhydroxides from the Endeavour segment, Juan de Fuca Ridge

We present first data on the geochemistry, mineralogy and morphology of near-vent sediments (35 and 200 m from active vent) and ridge flank sediments (approximately 3 km from the vent field) as well as oxyhydroxide deposits from the Endeavour segment, Juan de Fuca Ridge. The purpose of the study was to understand better the origin and characteristic features of metalliferous sediments associated with base and precious metal massive sulfides in volcanic terrains. Hydrothermal components in sediments are Fe-Si ± S-rich and Mn-Fe-Si-rich phases, sulfides and barite, which were exclusively derived from plume fallout. Sulfides are only a minor constituent of near-vent sediments (2-4 wt%) and were not detected in ridge flank sediments. The study suggests that the distribution of hydrothermal phases and associated elements in near-vent and ridge flank sediments is affected mainly by processes of agglomeration, dissolution, absorption and settling that take place within a plume and to a lesser extent post-depositional processes. Rapid deposition of sulfides in the vicinity of the vents is reflected in a sharp drop of the Cu concentrations in sediments with increasing distance from the vents. Besides sulfides, important carriers of Pb, Cu, Zn and Co in near-vent sediments are Fe-Mn oxyhydroxides that occur together with silica as aggregates of gel-like material and flaky particles and as coatings on filaments. Away from the vents, trace metals are mostly in Fe-Mn oxyhydroxides and authigenic Fe-rich montmorillonite. Oxyhydroxides at the Main Endeavour field are interpreted to have originated from oxidation of mound sulfides accompanied by precipitation of primary Fe-oxyhydroxide + silica from low-temperature fluids. At the Mothra field, seafloor deposits and chimney crusts composed of Fe-oxyhydroxide ± Mn + silica are considered to be direct precipitates from hydrothermal fluids that have been less diluted with seawater. Oxyhydroxide deposits exhibit unique microtextures that resemble mineralized microorganisms and may indicate existence of diverse microbial communities.     

High metal inputs to closed seas: the New Caledonian lagoon

The islands of New Caledonia are largely composed of ultrabasic rocks (peridotites). severily weathered, rich in Fe, Mn and Co, and where several ore deposits of Ni and Cr are extensively mined. Sediment cores from the bay of Dumbea, in the south of the main island, and from the northern part of the lagoon (Belep Islands), less affected by the mining activities, were analyzed for their mineral composition and metal concentrations. In the surficial sediments, oxides and silicates, including Fe serpentine and smectites, undergo rapid transformation or neoformation in a short time, in particular in the confined bay of Dumbea. Fe is largely present as goethite, and in deeper layers (60–100 cm) as hematite and magnetite. Chromite can be identified at each horizon. The metal concentrations decrease from the near shore areas, in particular the vicinity of the Dumbea river mouth to the open part of the lagoon. This trend is more important for Ni than for Fe or Cr. Fe ranges from 3.5 to 9% (dry weight), Ni from 200 to 2000 μg/g, Cr from 700 to 2000 μg/g, Co from 20 to 150 μg/g and Mn from 130 to 900 μg/g; yet the concentrations are lower than concentrations found in the ultrabasic rocks or laterites of the watershed. To try to understand the behavior of metals during the sedimentation-diagenesis events, we evaluated the sediment accumulation rate, and used different sequential leaching procedures. Fe, Mn, Ni, Cr and Co are mainly present as, or bound to, oxides or oxyhydroxides, even in the deeper layers ( > 100 cm) where the organic content is relatively high (about 6% of organic C). Metals are mainly transported from the land to the lagoon as oxides and dispersed in the lagoon sediments, where they are diluted with a large amount of carbonaceous sediment. During diagenesis, a significant part of Mn, Co and Ni are dissolved; but, unlike Mn and Co, which seem to coprecipitate with carbonate, most of the Ni is released into the waters of the lagoon. Apparently no horizon of the sediment has undergone significant in-situ metal enrichment.     

Absorption of metals on sedimentary and peat humic acids

Humic acids isolated from marine sediments were found to be effective in absorption of various metal ions through chelation, cation exchange and surface adsorption. The quantities of metal ions complexed varied from 40 to 205 mg/g of organic matter. In the presence of equal concentrations of Co, Cu, Mn, Ni and Zn in the reaction media, humic acid and peatmoss, a rich source of humic compounds, showed preferential absorption for Cu. Copper constituted more than 50% of the metal ions complexed by organic matter. As compared with the other metal ions, its bonding strength was very firm because it could not be displaced by ferric ion or cation exchange reagents.Peatmoss, a rich source of humic acid, was found to absorb significant quantities of various metal ions. Under laboratory conditions each kg of peat absorbed about 1500 mg of various metal ions from solutions containing equal concentrations of Co, Cu, Mn, Ni and Zn. However, in the field trials with sea water, absorption of metals was limited to Zn (28.7 mg/kg), Cu (3.66 mg/kg) and Fe (2.0 mg/kg). Under-saturation of sea water for transition metals and super-saturation for alkali and alkaline earth metals appears to be a bottleneck in the effective utilization of peat as a means of recovery of metals from sea water.     

Removal of trace metals by coprecipitation with Fe,Al and Mn from natural waters contaminated with acid mine drainage in the Ducktown Mining District,Tennessee

This study examined the sorption of trace metals to precipitates formed by neutralization of 3 natural waters contaminated with acid mine drainage (AMD) in the former Ducktown Mining District, Tennessee. The 3 water samples were strongly acidic (pH 2.2 to 3.4) but had distinctively different chemical signatures based on the mole fractions of dissolved Fe, Al and Mn. One sample was Fe-rich (Fe=87.5%, Al=11.3%, and Mn=1.3%), another was Al-rich (Al=79.4%, Mn=18.0%, and Fe=2.5%), and the other was Mn-rich (Mn=51.4%, Al=25.7%, and Fe=22.9%). In addition, these waters had high concentrations of trace metals including Zn (37,700 to 17,400 μg/l), Cu (13,000 to 270 μg/l), Co (1,500 to 520 μg/l), Ni (360 to 75 μg/l), Pb (30 to 8 μg/l), and Cd (30 to 6 μg/l). Neutralization of the AMD-contaminated waters in the laboratory caused the formation of either schwertmannite at pH<4 or ferrihydrite at pH>4. Both phases were identified by XRD analyses of precipitates from the most Fe-rich water. At higher pH values (∼5) Al-rich precipitates were formed. Manganese compounds were precipitated at pH∼8. The removal of trace metals depended on the precipitation of these compounds, which acted as sorbents. Accordingly, the pH for 50% sorption (pH₅₀) ranged from 5.6 to 7.5 for Zn, 4.6 to 6.1 for Cu, 5.4 to 7.7 for Ni, 5.9 to 7.9 for Co, 3.1 to 4.3 for Pb, and 5.5 to 7.7 for Cd. The pH dependence of sorption arose not only because of changes in the sorption coefficients of the trace metals but also because the formation and composition of the sorbent was controlled by the pH, the chemical composition of the water, and the solubilities of the oxyhydroxide-sulfate complexes of Fe, Al, and Mn.     

南极普里兹湾表层沉积物微量元素分布特征及其物源指示意义

利用电感耦合等离子体质谱仪测定了中国南极科考21~27航次期间获取的普里兹湾表层沉积物中Cu、Pb、Zn、Cd、Cr、Co、Al、Fe、Mn的含量,分析了普里兹湾微量元素的分布特征,结合沉积物粒度分布、生物硅含量,并利用富集系数和主成分分析的方法,探讨了微量元素的物源指示意义。研究结果表明:普里兹湾沉积物中的微量元素含量与南大洋其他海域具有很好的可比性。Cu、Zn、Cr、Co、Fe、Mn含量在陆坡深海区明显高于冰架边缘区和陆架区;Al、Pb含量在冰架边缘区较高;而Cd含量在陆架区相对较高。人类活动对普里兹湾沉积物中的微量元素没有明显的影响,南极大陆岩石风化产物和海洋生物源性沉降是其主要来源。冰架边缘区及陆架破折处P2-9站位的微量元素主要为岩源性输入。陆架区、陆坡深海区的微量元素Cu、Zn、Cr、Co、Fe、Mn明显受到生源性物质输入的影响。而普里兹湾沉积物中Cd则主要来源于硅藻的吸收利用及硅质软泥的富集。