Hydrochemical evidence for mixing of river water and groundwater during high-flow conditions, lower Suwannee River basin, Florida, USA

 Karstic aquifers are highly susceptible to rapid infiltration of river water, particularly during periods of high flow. Following a period of sustained rainfall in the Suwannee River basin, Florida, USA, the stage of the Suwannee River rose from 3.0 to 5.88 m above mean sea level in April 1996 and discharge peaked at 360 m³/s. During these high-flow conditions, water from the Suwannee River migrated directly into the karstic Upper Floridan aquifer, the main source of water supply for the area. Changes in the chemical composition of groundwater were quantified using naturally occurring geochemical tracers and mass-balance modeling techniques. Mixing of river water with groundwater was indicated by a decrease in the concentrations of calcium, silica, and ²²²Rn; and by an increase in dissolved organic carbon (DOC), tannic acid, and chloride, compared to low-flow conditions in water from a nearby monitoring well, Wingate Sink, and Little River Springs. The proportion (fraction) of river water in groundwater ranged from 0.13 to 0.65 at Wingate Sink and from 0.5 to 0.99 at well W-17258, based on binary mixing models using various tracers. The effectiveness of a natural tracer in quantifying mixing of river water and groundwater was related to differences in tracer concentration of the two end members and how conservatively the tracer reacted in the mixed water. Solutes with similar concentrations in the two end-member waters (Na, Mg, K, Cl, SO₄, SiO₂) were not as effective tracers for quantifying mixing of river water and groundwater as those with larger differences in end-member concentrations (Ca, tannic acid, DOC, ²²²Rn, HCO₃). Received, March 1999 / Revised, July 1999 / Accepted, July 1999     

Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water

Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO₃ electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu (⁶⁵Cu/⁶³Cu) and Zn (⁶⁶Zn/⁶⁴Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors (α_soln-solid) are 0.99927 ± 0.00008 for Cu and 0.99948 ± 0.00004 for Zn or, alternately, the separation factors (Δ_soln-solid) are −0.73 ± 0.08‰ for Cu and −0.52 ± 0.04‰ for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal-oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).     

Removal of dissolved boron and silicon during estuarine mixing of sea and river waters

The behaviour of dissolved boron and silicon during mixing of sea and river waters has been studied in two surveys of the estuary of the River Alde in Suffolk, England. Removal of approximately 25–30 per cent was found for both elements. This appears to be the first report of estuarine removal of dissolved boron. The extent of removal of silicon in the Alde is somewhat higher than that found in other estuaries.     

Dilution and removal of dissolved metals from acid mine drainage along Imgok Creek,Korea

The dilution factors (D_i) and removal fractions (R_i) of pollutants from acid mine drainage (AMD) were quantitatively estimated using two different methods, the conservative component and mass balance method, along Imgok Creek in Korea. The conservative component method assumes that SO₄ is a perfectly conservative component and calculates D_i and R_i from the concentration ratios of SO₄. The mass balance method solves the simultaneous equations relating the concentrations of dissolved components to their precipitation stoichiometries to obtain D_i and R_i. The results from both methods are little different, indicating that SO₄ concentration is a good indicator of dilution for Imgok creek. The calculated D_i's of pollutants quickly decrease from the site of AMD input to the site a few km downstream, but then remain more or less constant over the reaches farther downstream. This is because D_i loses its sensitivity in the reaches where difference in SO₄ concentration between the main stream and combining tributaries significantly diminishes. The calculated R_i's show that approximately 90, 95, and 75% of the original Fe input were removed from the streamwater in October 1996, April 1997, and October 1997, respectively. Aluminum was almost completely removed in April 1997, but only 50% of the original Al was removed in October 1997. The removal of Fe was due to the precipitation of schwertmannite or ferrihydrite and Al due to amorphous Al₄(OH)₁₀SO₄. The maximum removal fraction of dissolved SO₄ was only 5%. The other metals from AMD were significantly removed from the stream water only in April 1997. These metals were removed not by precipitation but by adsorption on and/or coprecipitation with Fe/Al-compounds. The relatively abundant freshwater supply in April 1997 might raise stream pH higher than the adsorption edge and consequently, contribute to rapid metal attenuation by forcing not only more precipitation but also more adsorption of the dissolved metals.     

Characterization of limestone reacted with acid-mine drainage in a pulsed limestone bed treatment system at the Friendship Hill National Historical Site,Pennsylvania, USA

Armoring of limestone is a common cause of failure in limestone-based acid-mine drainage (AMD) treatment systems. Limestone is the least expensive material available for acid neutralization, but is not typically recommended for highly acidic, Fe-rich waters due to armoring with Fe(III) oxyhydroxide coatings. A new AMD treatment technology that uses CO₂ in a pulsed limestone bed reactor minimizes armor formation and enhances limestone reaction with AMD. Limestone was characterized before and after treatment with constant flow and with the new pulsed limestone bed process using AMD from an inactive coal mine in Pennsylvania (pH=2.9, Fe =150 mg/l, acidity =1000 mg/l CaCO₃). In constant flow experiments, limestone is completely armored with reddish-colored ochre within 48 h of contact in a fluidized bed reactor. Effluent pH initially increased from the inflow pH of 2.9 to over 7, but then decreased to <4 during the 48 h of contact. Limestone grains developed a rind of gypsum encapsulated by a 10- to 30-μm thick, Fe-Al hydroxysulfate coating. Armoring slowed the reaction and prevented the limestone from generating any additional alkalinity in the system. With the pulsed flow limestone bed process, armor formation is largely suppressed and most limestone grains completely dissolve resulting in an effluent pH of >6 during operation. Limestone removed from a pulsed bed pilot plant is a mixture of unarmored, rounded and etched limestone grains and partially armored limestone and refractory mineral grains (dolomite, pyrite). The ∼30% of the residual grains in the pulsed flow reactor that are armored have thicker (50- to 100-μm), more aluminous coatings and lack the gypsum rind that develops in the constant flow experiment. Aluminium-rich zones developed in the interior parts of armor rims in both the constant flow and pulsed limestone bed experiments in response to pH changes at the solid/solution interface.     

Fluid infiltration and regional metamorphism of the Waits River Formation, north-east Vermont, USA

Abstract The Siluro-Devonian Waits River Formation of north-east Vermont was deformed, intruded by plutons and regionally metamorphosed during the Devonian Acadian Orogeny. Five metamorphic zones were mapped based on the mineralogy of carbonate rocks. From low to high grade, these are: (1) ankerite-albite, (2) ankerite-oligoclase, (3) biotite, (4) amphibole and (5) diopside zones. Pressure was near 4.5kbar and temperature varied from c. 450° C in the ankerite-albite zone to c. 525° C in the diopside zone. Fluid composition for all metamorphic zones was estimated from mineral equilibria. Average calculated χ_co2[= CO₂/(CO₂+ H₂O)] of fluid in equilibrium with the marls increases with increasing grade from 0.05 in the ankerite-oligoclase zone, to 0.25 in the biotite zone and to 0.44 in the amphibole zone. In the diopside zone, χ_CO2 decreases to 0.06. Model prograde metamorphic reactions were derived from measured modes, mineral chemistry, and whole-rock chemistry. Prograde reactions involved decarbonation with an evolved volatile mixture of χ_CO2 > 0.50. The χ_CO2 of fluid in equilibrium with rocks from all zones, however, was generally <0.40. This difference attests to the infiltration of a reactive H₂O-rich fluid during metamorphism. Metamorphosed carbonate rocks from the formation suggests that both heat flow and pervasive infiltration of a reactive H₂O-rich fluid drove mineral reactions during metamorphism. Average time-integrated volume fluxes (cm³ fluid/cm² rock), calculated from the standard equation for coupled fluid flow and reaction in porous media, are (1) ankerite-oligoclase zone: c. 1 × 10⁴; (2) biotite zone: c. 3 × 10⁴; (3) amphibole zone: c. 10 × 10⁴; and diopside zone: c. 60 × 10⁴. The increase in calculated flux with increasing grade is at least in part the result of internal production of volatiles from prograde reactions in pelitic schists and metacarbonate rocks within the Waits River Formation. The mapped pattern of time-integrated fluxes indicates that the Strafford-Willoughby Arch and the numerous igneous intrusions in the field area focused fluid flow during metamorphism. Many rock specimens in the diopside zone experienced extreme alkali depletion and also record low χ_CO2. Metamorphic fluids in equilibrium with diopside zone rocks may therefore represent a mixture of acid, H₂O-rich fluids given off by the crystallizing magmas, and CO₂-H₂O fluids produced by devolatilization reactions in the host marls. Higher fluxes and different fluid compositions recorded near the plutons suggest that pluton-driven hydrothermal cells were local highs in the larger regional metamorphic hydrothermal system.     

Effect of pH and salinity on flocculation process of heavy metals during mixing of Aras River water with Caspian Sea water

The flocculation process of metals can play an effective and important role in self-purification of metals during the mixing of freshwater with seawater in estuary. Such processes are of highly ecological and biological importance. The present study deals with the effect of pH and salinity on the flocculation process of dissolved Cu, Mn, Ni, Zn and Pb on a series of mixtures with salinities ranging from 0.5 to 2.5 ‰ with various pHs values (pH 7, 7.5 and 8) during the mixing of the Aras River water with the Caspian Sea water. The flocculation trend of Pb (100 %) > Ni (62.5 %) > Zn (30.43 %) > Mn (25 %) > Cu (18.18 %) at different salinity regimes (0.5–2.5 ‰) at pH 7, indicates well that Pb, Ni, Zn and Mn have non-conservative behavior and Cu has relatively conservative behavior. At various salinity ranges (0.5–2.5 ‰) and pH 7.5, the flocculation trend of Pb (100 %) > Ni (62.5 %) > Mn (37.5 %) > Cu (24.24 %) > Zn (17.39 %) indicates that Pb, Ni, Mn and Cu have non-conservative behavior and Zn has relatively conservative behavior. Also, the flocculation trend of Pb (100 %) > Zn (78.26 %) > Ni (62.5 %) > Mn (37.5 %) > Cu (15.15 %) at different salinities (0.5–2.5 ‰) and pH 8, indicates that Pb, Zn, Ni and Mn have non-conservative behavior and Cu has relatively conservative behavior. Cluster analysis indicates Mn and Ni are mainly governed by salinity. According to the mean annual discharge of the Aras River (5,323 × 10⁶ m³/year), the annual discharge of dissolved Cu, Mn, Ni, Zn and Pb into the Caspian Sea would reduce from 175.66, 85.17, 85.17, 1,224.29 and 53.23 to 149.04, 53.23, 31.94, 266.15 and 0.00 ton/year, respectively.     

Prevention of well clogging during aquifer storage of turbid tile drainage water rich in dissolved organic carbon and nutrients

Well clogging was studied at an aquifer storage transfer and recovery (ASTR) site used to secure freshwater supply for a flower bulb farm. Tile drainage water (TDW) was collected from a 10-ha parcel, stored in a sandy brackish coastal aquifer via well injection in wet periods, and reused during dry periods. This ASTR application has been susceptible to clogging, as the TDW composition largely exceeded most clogging mitigation guidelines. TDW pretreatment by sand filtration did not cause substantial clogging at a smaller ASR site (2 ha) at the same farm. In the current (10 ha) system, sand filtration was substituted by 40-μm disc filters to lower costs (by 10,000–30,000 Euro) and reduce space (by 50–100 m²). This measure treated TDW insufficiently and injection wells rapidly clogged. Chemical, biological, and physical clogging occurred, as observed from elemental, organic carbon, 16S rRNA, and grain-size distribution analyses of the clogging material. Physical clogging by particles was the main cause, based on the strong relation between injected turbidity load and normalized well injectivity. Periodical backflushing of injection wells improved operation, although the disc filters clogged when the turbidity increased (up to 165 NTU) during a severe rainfall event (44 mm in 3 days). Automated periodical backflushing, together with regulating the maximum turbidity (<20 NTU) of the TDW, protected ASTR operation, but reduced the injected TDW volume by ~20–25%. The studied clogging-prevention measures collectively are only viable as an alternative for sand filtration when the injected volume remains sufficient to secure the farmer’s needs for irrigation.

     

西北内陆河流域的水资源利用及生态环境保护

内陆河流域是我国西北最具有发展潜力的地区之一，水资源及脆弱的生态环境是制约这一地区社会经济发展的最重要因素，本文在分析西北内陆河流域水资源状况及面临的主要问题的基础上，提出了解决水资源供需矛盾，实现水资源合理利用及加强生态环境保护建设的对策建议。     

Syn-tectonic pluton intrusion during contractional deformation: microstructural and metamorphic evidence from the aureole of the Acadian Victory Pluton, north-eastern Vermont, USA

Structures within the aureole of the Acadian (Devonian) Victory Pluton suggest that movement along the Monroe Fault occurred during pluton intrusion. Pre- or syn-tectonic garnet textures, including discordant internal and external foliations, sigmoidal inclusion trails and deflection of the matrix foliation around garnet, are found along the Monroe Fault. In sillimanite+K-feldspar grade rocks, the matrix foliation, defined by biotite and fibrolitic sillimanite, wraps around garnet and sillimanite porphyroblasts. Granite dykes and sills near the pluton contact are folded and boundinaged, and leucosome fills garnet pressure shadows and shear bands. Away from the fault and pluton contact, microstructures indicate much less deformation during metamorphism, suggesting that deformation was partitioned into the fault or the pluton. Deformation ceased before crystallization of the main body of the Victory Pluton was complete. It is possible that magmatism facilitated deformation along the Monroe Fault, and/or that the magma was transported to the mid- to upper crust along the Monroe Fault. This study suggests that Acadian deformation in north-eastern Vermont occurred as late as 390–370  Ma.     

Diurnal variations in,and influences on,concentrations of particulate and dissolved arsenic and metals in the mildly alkaline Wallkill River,New Jersey,USA

Diurnal variations in particulate and dissolved As and metal concentrations were observed in mildly alkaline water from a wetlands site on the Wallkill River in northwestern New Jersey. The site, underlain by glacial sediments over dolomite bedrock, is 10 km downstream from a mined area of the Franklin Marble, host to Zn ores, also As and Mn minerals. In mid-September 2005, maxima and minima in dissolved-oxygen-concentration and pH, typically caused by photosynthesis and respiration, occurred at 2000 and 0800 hours. Concentrations of dissolved As (1.52–1.95 μg/L) peaked at dusk (2000 hours), whereas dissolved Mn and Zn concentrations (76.5–96.9 and 8.55–12.8 μg/L, respectively) were lowest at dusk and peaked at 1000 hours. These opposing cycles probably reflect sorption and desorption of As (an anion), and Mn and Zn (cations) as pH varied throughout the 24-h period. Doubly-peaked cycles of B, Cl, SO₄, and nutrients also were observed; these may result from upstream discharges of septic-system effluent. Both recoverable amd particulate Al, Fe, Mn, and Zn concentrations peaked between 0200 and 0600 hours. The particulate metals cycle, with perturbations at 0400 hours, may be influenced by biological activity.     

The behaviour of the rare earth elements during mixing of river and sea waters

Rare earth element concentrations have been measured in organic-rich Luce river water and coastal sea water. Concentrations (e.g. ～350?1850 pmol/kg Nd in the Water of Luce and ～45?350 pmol/ kg Nd in Luce Bay) are related to the presence of particles, with 30–60% of the REE associated with >0.4?0.7 μm particles, and to riverine Fe concentrations. REE fractionation occurs in the river water the submicrometre river water is heavy REE enriched whereas the coarser fraction has a more shale-like REE pattern.Laboratory experiments show that the REE in organic-rich river waters are chiefly associated with Feorganic matter colloids which flocculate during estuarine mixing. Preferential removal of heavy REE (～95%) relative to light REE (～60%) occurs, but no Ce anomaly is developed. In contrast, no REE removal occurs during estuarine mixing with organic-poor river water.     

重庆老龙洞地下河间隙水重金属污染及毒性评估

为查明重庆岩溶地区老龙洞地下河重金属污染情况,于2013年9月采集了地下河上覆水体和表层沉积物间隙水共7组水样,用ICP-OES测定地下河上覆水体和表层沉积物间隙水中的Mn含量,ICP-MS测定Cu、Cd、Cr、As和Pb含量,分析了老龙洞地下河表层沉积物间隙水中各重金属元素的空间分布,对不同介质中的重金属元素进行相关性分析,并参考美国EPA推荐的“国家推荐水质标准”对间隙水中重金属可能产生的生物毒性进行评估。结果表明：老龙洞地下河上覆水体中Mn和Pb的浓度超过了GB 5749-2006规定的生活饮用水限值（Mn≤100 ug/L,Pb≤10 ug/L）,不可作为饮用水源;间隙水中各重金属元素的浓度都比上覆水体高,有向上覆水体扩散的潜在可能性。除Pb、Mn外,间隙水中重金属的含量大小依次为上游>中游>下游。上覆水中除Mn与As、Cd与Cr外,其他金属元素之间的相关性不大;间隙水中Cr、Cu、As和Cd的相关系数分别为0.895～0.997,呈高度正相关。间隙水中金属元素除As不会对水生生态系统产生急性毒性外,Cr、Cu、Cd和Pb都会对水生生态系统产生急性毒性,尤以Cr、Cu、Cd最为严重。     

Distribution and behavior of heavy metals in a river polluted by acid mine drainage in the Dabaoshan mine area, China

Acid mine drainage （AMD） has been recognized as a major environmental pollution problem over past decades. This pollutant effluent is complex and is characterized by elevated concentrations of iron and sulfate, low pH, and high concentrations of a wide variety of metals depending on the host rock geology. Massive inadvertent discharges from acid mines have given rise to dramatic cases of ecological damage. These events indicate an improved understanding of the mechanism controlling metal transport to the river is important, since the aquatic ecology will be affected, to some degree, dependent on the phase （dissolved or particulate） in which the metal is transported. In this study, polluted water samples were collected along the Hengshi River near the Dabaoshan mine, Guangdong, China, in April 2005. The concentrations of dissolved Cu, Zn, Cd and Pb have been determined using ICP-MS and the chemical speciation of those metals in suspended particles was examined using BCR methods and SEM/EDX mineralogical analysis. Combining these two sets of data, the intention was to develop geochemical concepts, which explain the behavior of Cu, Zn, Cd and Pb in particle-water interactions of heavy metals in AMD. The results show that the dissolved heavy metals exhibited non-conservative behavior in the Hengshi River. The dissolved and particulate Cu, Zn, Cd and Pb have the similar spatial distribution, which decreased gradually along the river except in the lower reaches because of the absorption-desorption between dissolved and particulate phases. Although the metal concentrations in both phases were elevated, dissolved metals were dominant and had the maximum concentrations in the low pH region.     

Distribution and speciation of metals,phosphorus, sulfate and organic material in brackish estuary water affected by acid sulfate soils

Dissolved (<1 kDa) and colloidal (1 kDa-0.45 μm) size fractions of sulfate, organic carbon (OC), phosphate and 17 metals/metalloids were investigated in the acidic Vörå River and its estuary in Western Finland. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these waters. The sampling was carried out during high-water flow in autumn and in spring when the abundantly occurring acid sulfate (AS) soils in the catchment area are extensively flushed. Based on the high concentrations of sulfate, acidity and several metals, it is clear that the Vörå River and its estuary is strongly affected by AS soils. The high dissolved form of metals limits also the existence of fish and other organisms in this estuary, and certainly also in other similar shallow brackish estuaries elsewhere in the Gulf of Bothnia. However, generally already <20% saline sea water reduces the concentration for OC and several elements (Al, Cu, Cr, Fe, Pb, PO₄ and U) by half and c. 20–30% saline sea water is needed to halve concentrations of Cd, Co, Mn, Ni and Zn. Consequently, these elements as well as organic matters were rapidly precipitated in the estuary, even after mixing with fairly small amounts of the alkaline brackish sea water. Aluminium, Cu, Fe and U most likely precipitate together with organic matter closest to the river mouth. Manganese is relatively persistent in solution and, thus, precipitates further down the estuary as Mn oxides, which concomitantly capture Ba, Cd, Co, Cu, Ni and Zn. In the inner estuary, the high contents of Al is as important than Fe in removing PO₄ and, thus, also reducing the risk of algae blooms in near coastal areas influenced by AS soils in the Gulf of Bothnia. Moreover, the dispersion of metals far out in the estuary is dependent on hydrological conditions, i.e. with high flows the plume of metal-rich water will spread further out in the estuary. Furthermore, the extensive drainage of the catchment and subsequent artificial enlargement of the river channel during recent decades has not only enabled oxidation of sulfidic sediments, but strongly increased flow peaks that reach further out in the estuary.     

Distribution and storage of sediment-associated heavy metals downstream of the remediated Rum Jungle Mine on the East Branch of the Finniss River,Northern Territory,Australia

Instream, overbank and cut riverbank exposures along the East Branch of the Finniss River downstream of Rum Jungle Mine, Northern Territory have been analysed for their total metal concentrations using instrumental neutron activation analysis (INAA). Concentration values for the < 62.5 μm and bulk sample fractions are compared to Australian sediment quality guidelines values (ANZECC/ARMCANZ, 2000). The results reveal that channel and overbank environments are contaminated with heavy metals, with many samples exceeding the low and high sediment guidelines values. The < 62.5 μm fraction is consistently more contaminated than bulk samples as are instream environments compared to adjacent overbank environments. Metal concentrations are strongly correlated to sediment pH and Fe values, suggesting that these variables are significant in controlling the spatial distribution of sediment-associated metals. The strong positive correlation between sediment-associated metals and Fe is probably related to the process of metal sequestration by Fe (and Mn) oxyhydroxides. The spatial distribution of sediment-associated metals downstream of the Rum Jungle Mine site does not display a simple distance–metal concentration decay pattern. It is suggested that the non-uniform spatial distribution of sediment-associated metals is a function of local, reach-scale variations in channel geometry and geomorphology, which control sediment storage and transfer patterns. In cut riverbank exposures the vertical of metals distribution is non-uniform and probably reflects differential metal mobility. Despite rehabilitation of the mine site in the 1980s, the elevated sediment-associated metal concentrations that remain within the East Branch of the Finniss River system are likely to render the system contaminated for the foreseeable future and limit the potential for the full recovery of aquatic and terrestrial flora and fauna.     

滇西沘江流域水体中重金属元素的地球化学特征

通过测定流经兰坪金顸铅锌矿区的沘江水体中Pb、Zn、Cd、As的含量和底泥中重金属元素的化学形态的含量,分析了重金属元素的分布和化学形态的变化。结果表明,沘江水遭到了Cd污染,底泥已经成为重金属元素的蓄积库,以国家土壤环境质量标准（Ⅲ级）衡量,Pb、Zn、Cd和舡分别超标3．4倍、15．8倍、106倍和2．6倍。沘江水中重金属元素含量的峰值在矿山附近的下游,而底泥中重金属元素的峰值在矿山下游30-50km的地方,矿业活动、水流变缓、pH等水体环境条件的变化都能影响水和底泥中重金属元素的含量。底泥中的Pb以碳酸盐结合态为主,Zn和Cd以铁锰氧化物结合态为主,而As以残渣态为主。Pb、Cd、Zn三种元素的环境有效态含量比较高,对沘江流域生态环境具有潜在的巨大的危害。