Geology topics

Richard B. Wanty

Publications and source records attributed to Richard B. Wanty.

At least 19 recordsLinked to original sources

USGS2026

Distinguishing natural from mining-related metal sources by including streambank groundwater data in a stream mass loading study

Distinguishing stream metal loading caused by mine features from that caused by natural background sources remains challenging, yet this distinction is essential for making effective remedial decisions at many legacy mine sites. We combine a stream tracer injection and synoptic sampling study with data from shallow near-stream groundwater wells to estimate left-bank versus right-bank metal loading contributions at the 100-m spatial scale. The study was performed in the East Mancos River, a mountain headwater stream in Colorado, USA. The dominant source of elevated stream metal concentrations could be either groundwater infiltration through right-bank Doyle Mine waste piles or natural acid rock drainage from hydrothermally altered bedrock located mainly on the left bank. For the five metals of concern (Cu, Al, Zn, Cd, and Mn), we find that 15 % of the load contributed by diffuse groundwater inputs in the section potentially influenced by Doyle mine waste originates from the right bank. This right-bank potential mine contribution equates to only 3 % of the total watershed instream load for these metals. Furthermore, apparent 3 H/ 3 He groundwater ages in segments contributing most of the right-bank metal loading are sufficiently old (9–12 yr) to suggest that infiltration through the waste piles, located only 140–180 m from the stream, is unlikely. Estimated potential Doyle mine loading contributions can therefore be considered maximum values. Study results thus indicate that Doyle mine waste piles are a minor source of metal loading under low-flow conditions, and streambank groundwater data can provide valuable additional information in stream mass loading studies.

Colorado↗

USGS2022

Incorporating streambank wells in stream mass loading studies to more effectively identify sources of solutes in stream water

Stream synoptic sampling studies that include flow estimates derived from the stream tracer dilution method are now commonly performed to identify sources and processes controlling solute transport to streams. However, a limitation of this mass-loading approach is its inability to identify the side of the stream on which a source is located in the common case where loading is largely from groundwater discharge. Such bank-specific loading information can be particularly valuable at mining-affected sites where both mining-related and natural background metal sources are often closely intermingled. Here we combine the stream mass-loading approach with data from pairs of shallow hand-installed streambank wells located on opposite sides of a gaining metal-impacted headwater stream to estimate bank-specific metal loading rates. Study results successfully identify a right-bank zone in the upper half of the primary study reach as the dominant source of loading, where groundwater discharge is elevated in metals due to natural weathering of sulfide-rich bedrock. A left-bank zone in the lower half of the primary study reach was also identified as a secondary, yet still substantial, loading source, where groundwater is likely impacted by portal discharge and/or waste piles associated with an adjacent abandoned mine. Determining the dominance of the left-bank mining-related source compared to other potential right-bank natural sulfide weathering sources would not have been possible without the streambank wells. Streambank wells also enabled collection of dissolved gas samples for groundwater dating. Computed piston-flow 3 H/ 3 He groundwater ages show little to no correlation with either metal concentrations or loading rates, suggesting that groundwater residence time and flow path variations exert little influence on groundwater discharge chemistry compared to variations in bedrock and soil composition. This study thus provides proof of concept that the proposed method of combining streambank well data with stream tracer injection and synoptic sampling can provide useful information on bank-specific mass loading rates and sources of contaminants affecting stream water quality.

Colorado↗

USGS2021

Direct observation of the depth of active groundwater circulation in an alpine watershed

The depth of active groundwater circulation is a fundamental control on stream flows and chemistry in mountain watersheds, yet it remains challenging to characterize and is rarely well constrained. We collected hydraulic conductivity, hydraulic head, temperature, chemical, noble gas, and 3 H/ 3 He groundwater age data from discrete levels in two boreholes 46 and 81 m deep in an alpine watershed, in combination with chemical and age data from shallow groundwater discharge, to discern groundwater flow rates at different depths and directly observe active and inactive groundwater. Vertical head gradients are steep (average of 0.4) and thermal profiles are consistent with typical linear conductive continental geotherms. Groundwater deeper than ∼20 m is distinct from shallow groundwater and creek water in its chemistry, noble gas signature, and age (dominantly >65 years compared to <9 years). Together these results suggest low vertical groundwater flow velocities and a relatively shallow active circulation depth of ∼20 m. This hypothesis is tested with a simple 2‐D numerical fluid flow and heat transport model representing a hillslope transect through the two boreholes. The modeling indicates that the subhorizontally bedded sedimentary rocks underlying the basin are highly anisotropic with low vertical hydraulic conductivity, and at most ∼10% of bedrock recharge (equivalent to <2% of stream baseflow) flows below a depth of 20 m. The study demonstrates the considerable value of discrete‐depth hydrogeologic, chemical, and age data for determining active circulation depth, and illustrates an approach for maximizing the utility of individual boreholes drilled for mountain bedrock aquifer characterization.

Colorado↗

USGS2021

Regional occurrence of aqueous tungsten and relations with antimony, arsenic and molybdenum concentrations (Sardinia, Italy)

T ungsten (W) is rarely found in natural waters, yet it can be introduced into the food chain and cause potentially toxic effects. Uptake of W by plants and vegetables, or trace presence of W in drinking water are possible vectors for ingestion of W by humans. The latter is recognized as a possible cause of lymphatic leukemia. Increased uses of W might result in a degradation of water resources, with attendant adverse effects on biota and human health. Therefore, this study was aimed at investigating regional occurrence and speciation of W in aquatic systems in Sardinia, Italy, factors affecting W mobility and possible relations with other oxyanion-forming trace elements such as Sb, As and Mo. Although our results are specifically from Sardinia, the implications are broader and should prompt future studies in other areas with known high W concentrations. A total of 350 sample sites are reported here, including surface waters, groundwaters, mine drainages, thermal waters and local seawater. The waters were analyzed for major and trace components, including W, Sb, As and Mo. The waters showed a variety of major chemical compositions and W concentrations. High concentrations of W were found in some mine waters and drainages from slag heaps, with W, Sb and As up to 140, 5000 and 800 μg L −1 , respectively. The highest concentrations of W occurred under slightly alkaline pH and oxygenated conditions, and were likely due to the dissolution of scheelite [CaWO 4 ] hosted in materials with which the water came into contact. High W concentrations also were observed in thermal waters, under alkaline pH and reducing conditions, and sometimes coincided with relatively high concentrations either of As or Mo. Previous studies of W geochemistry have focused on WO 4 2− as the major dissolved form of W. For this study, we have augmented the thermodynamic database in PHREEQC to include possible formation of many other W-bearing complexes gleaned from the literature. The results of the speciation calculations with the newly added complexation reactions shows that the neutral species CaWO 4 ° and MgWO 4 ° are particularly dominant in most W-bearing waters and lead to undersaturation with respect to scheelite and other W-bearing minerals. Assessing W contamination in water systems and establishing W limits in drinking water may prevent potential adverse effects of W on human and ecosystem health.

Sardinia↗

USGS2021

Variation in metal concentrations across a large contamination gradient is reflected in stream but not linked riparian food webs

Aquatic insects link food web dynamics across freshwater-terrestrial boundaries and subsidize terrestrial consumer populations. Contaminants that accumulate in larval aquatic insects and are retained across metamorphosis can increase dietary exposure for riparian insectivores. To better understand potential exposure of terrestrial insectivores to aquatically-derived trace metals, metal concentrations in water and tissues were analyzed from different components of streams and riparian food webs across a large (2–3 orders of magnitude) metal gradient (e.g., Zn, Cu, Cd, Pb) in the Rocky Mountains (USA). Our research indicates that the trace metal concentration gradient present among streams was lost during metamorphosis of aquatic larval insects into terrestrially flying adults, decoupling terrestrial exposures from aquatic concentrations. This pattern was caused by declines in 1) among-stream variation in trace metal concentrations, 2) relationships between metal concentrations in paired water and food web components, and 3) mean metal concentrations within aquatic food webs and across the aquatic-terrestrial boundary. Specifically, among-stream variation in trace metal concentrations was highest for water and aquatic vegetation, intermediate for aquatic insect larvae (~30% lower than water) and lowest for adult aquatic insects and riparian spiders (~65% lower). Metal concentrations in paired water and food web components ranged from highly related across the stream-metal gradient (slopes ~1) for water and aquatic vegetation, to less related (slopes closer to 0) for aquatic vegetation and aquatic insect larvae, to unrelated (slopes ~0) for aquatic larval and adult insects. Finally, mean metal concentrations were highest in aquatic vegetation and lowest in adult aquatic insects emerging from streams (~50% lower than aquatic vegetation). Our results indicate less efficient trophic transfer and higher metamorphic loss of trace metals from high metal streams (i.e., exposure-dependent transfer). For many trace metals, aquatic-terrestrial dietary transfer is unlikely to be an important source of exposure for terrestrial insectivores of adult aquatic insects.

Science of the Total Environment↗

USGS2020

Natural attenuation can lead to environmental resilience in mine environment

Four streams flowing in the Iglesiente and Arburese mine districts (SW Sardinia, Italy), exploited for zinc (Zn) and lead (Pb) extraction from sulphides and secondary non-sulphide mineralization (calamine ores), have been studied combining investigations from the macroscale (hydrologic tracer techniques) to the microscale (X-ray powder diffraction, scanning electron microscopy, X-ray absorption spectroscopy). In the investigated area, concerns arise from release of metals to water during weathering of ore minerals and mine-waste. Specifically, Zn is observed at extremely high concentrations (10s of mg/L or more) in waters in some of the investigated catchments. The results from synoptic sampling campaigns showed marked differences of Zn loads, from 6.3 kg/day (Rio San Giorgio) to 2000 kg/day (Rio Irvi). Moreover, natural attenuation of metals was found to occur i) through precipitation of Fe compounds (Fe oxy/hydroxides and “green rust”), ii) by means of the authigenic formation of metal sulphides promoted by microbial sulphate reduction, iii) by metal intake in roots and stems of plants ( Phragmites australis and Juncus acutus ) and by immobilization in the rhizosphere, and iv) by cyanobacterial biomineralization processes that lead to formation of Zn-rich phases (hydrozincite and amorphous Zn-silicate) The biologically mediated natural processes that lead to significant abatement and/or reduction of metal loads, are the response of environmental systems to perturbations caused from mine activities, and can be considered part of the resilience of the system itself. The aim of this study is to understand the effect of these processes on the evolution of the studied systems towards more stable and, likely, resilient conditions, e.g. by limiting metal mobility and favoring the improvement of the overall quality of water. The understanding of how ecosystems adapt and respond to contamination, and which chemical and physical factors control these natural biogeochemical barriers, can help to plan effective remediation actions.

Sardinia↗

USGS2019

A 20-year record of water chemistry in an alpine setting, Mount Emmons, Colorado, USA

From 1997 to the present, the U.S. Geological Survey and other agencies have been collecting water samples for chemical analyses on Mount Emmons in central Colorado, USA. The geology of Mount Emmons is dominated by Upper Cretaceous to Paleogene sediments of marine to continental origin, with felsic intrusive rocks interrupting the sedimentary block. Extensive sulphide-rich alteration accompanied the intrusive events and forms an alteration halo in the sediments. Weathering of these sulphide minerals has led to numerous springs and seeps with a naturally low pH and high concentrations of metals, especially Fe and Zn. Superimposed on the natural geochemical signature are acid, metal-rich drainages from several mines and drill holes. Thus, streams on Mt. Emmons have a mix of natural and anthropogenic metal sources. Nearly 450 samples compose the database, with numerous sample locations replicated from the late 1990s to the present. Although there does not appear to be any temporal pattern in the data, consistent spatial variations are observed that allow us to characterize the natural and anthropogenic water sources.

Colorado↗

USGS2019

Aluminum mobility in mildly acidic mine drainage: Interactions between hydrobasaluminite, silica and trace metals from the nano to the meso-scale

Aluminum precipitates control the hydrochemistry and mineralogy of a broad variety of environments on Earth (e.g., acid mine drainage, AMD, coastal wetlands, boreal and alpine streams, tropical acid sulfate soils, laterites and bauxites, …). However, the geochemical and mineralogical processes controlling Al (and other associated metals and metalloids) transport and removal in those environments are not fully understood. The geochemical system of Paradise Portal (Colorado, USA) comprises sulfate-rich mildly acidic waters, the hydrochemistry of which is directly controlled by the massive precipitation of hydrobasaluminite Al 4 (SO 4 )(OH) 10 ·12-36H 2 O. Three connected but discernible aluminum precipitation stages were identified and described: 1) nanoparticle formation and size decrease along the creek, 2) hydrobasaluminite neoformation on the riverbed, and 3) precipitate accretion and accumulation on the riverbed leading to Al and Fe banded formations. The co-occurrence of Al and Si in the system was observed, recording significant amounts of Si accompanying the three different components of the system (i.e., nanoparticles and fresh and aged Al-precipitates). Also, abrupt and minor changes in the sedimentary record were described and proposed to be the response of the system to seasonal and interannual changes in AMD chemistry. Concerning the mobility of other metals and metalloids, P, Th, V, W, Ti and B showed a tendency to be preferentially incorporated into hydrobasaluminite, while others like Be, As, Se or Ba tend to remain dissolved in the water.

Chemical Geology↗

USGS2019

Using stream-side groundwater discharge for geochemical exploration in mountainous terrain

Groundwater chemistry has been predominantly used in geochemical exploration studies to identify mineralized targets concealed under transported cover in areas with gentle topography. Another potentially valuable ap-plication that has received little attention is using groundwater chemistry to identify deposits concealed within mountain ridges. A number of geochemical exploration studies have employed surface water chemistry in hilly and mountainous terrain and have demonstrated mixed success. However, groundwater chemistry is potentially a more reﬁned and powerful tool because groundwater sample locations can be selected to target a speciﬁc hillslope zone, whereas surface water integrates the geochemical signature of the entire watershed area above the sample site. In this study, we propose an approach that utilizes shallow groundwater samples collected from near-stream, hand-installed sampling points. We tested this approach in Handcart Gulch, an unmined catchment in the Montezuma Mining District, Colorado, USA, where previous studies suggested the possible presence of a concealed mineral occurrence. Seventeen near-stream mini-boreholes were drilled in a stream-parallel 3.3-km-long transect to depths of ~2 m in ferricrete (iron-oxide cemented colluvium and alluvium) using a handheld rock-coring drill. Groundwater in the mini-boreholes was sampled for major and trace element chemistry, as well as environmental tracers including stable water isotopes, dissolved noble gases, helium isotopes, and tritium, to identify possible variations in groundwater age and recharge conditions/sources. Chemistry data delineate a well-deﬁned 900-m-wide zone of elevated SO4, Cu, and other metal concentrations on the east side of the stream. In this zone, Cu concentrations up to 2670 μg/L are 1–3 orders of magnitude greater than concentrations in upstream and downstream areas. Environmental tracer data show no corresponding anomalies in groundwater age or recharge conditions/sources within the zone, suggesting that the source of the elevated metals is a change in bedrock mineralogy as opposed to other hydrologic factors. The groundwater samples therefore successfully identify and reﬁne the location of a potential concealed high-Cu mineral occurrence in the watershed, de-monstrating that near-stream groundwater discharge may be a valuable medium for geochemical exploration in mountainous areas.

Colorado↗

USGS2018

Application of hydrologic-tracer techniques to the Casargiu adit and Rio Irvi (SW-Sardinia, Italy): Using enhanced natural attenuation to reduce extreme metal loads

Hydrologic tracer techniques were applied to Rio Irvi (SW Sardinia), a stream affected by mine drainage, allowing the calculation of stream discharge and metal loads and comparison to other streams. The calculated discharge showed a continuous increase from near 21.2 L/s to 29.1 L/s. Cumulative loads of mine-related constituents, including the Casargiu adit inflow, were large, with more than 9900 kg/day of SO 4 2− , 2370 kg/day of Zn, 550 kg/day of Fe and 172 kg/day of Mn. The greatest measurable inflow source of metals, other than the Casargiu adit, was an acidic tributary (L4), but most sources of instream metal load were related to dispersed groundwater inflows. Some of those groundwater inflows were related to non-flowing tributaries. Calculations of the cumulative instream metal load, excluding the Casargiu adit inflow, indicated increases of 1250 kg/day for SO 4 2 , 858 kg/day for Zn - , 137 kg/day gain for Fe and 60 kg/day for Mn. Rio Irvi Zn load was extreme for a stream of this size and discharge. A comparison with two other mine-affected rivers in Sardinia indicated the loading in Rio Irvi was two to three orders of magnitude greater. This difference was attributed to different geochemical conditions, but also to a lack of a biogeochemical barrier like that seen to be acting along and below the riverbed in Rio San Giorgio. Several years of intense vegetation growth in the river bed of Rio San Giorgio created a biogeochemical barrier to metal loading, and the cumulative Zn load there was near 8 kg/day, despite being a drainage with a greater mass of mine wastes to contribute to the load.

Sardinia↗

USGS2017

Using large databases of groundwater chemistry in the northern Midwest USA: The effects of geologic and anthropogenic factors

Regional geochemical databases for the northern Midwest USA are being compiled to examine the various geogenic and anthropogenic factors that control the chemistry of groundwater. At the regional scale, variations are seen that are attributable to agricultural and urban effects, or to geologic factors. Examples of the former include enrichments of nitrate in groundwater, while examples of the latter mainly highlight geochemical differences between carbonate rocks and all other rock types in the region. This paper examines a few of these regional effects and the spatial scales at which they can be observed.

Article↗

USGS2017

In vivo isotopic fractionation of zinc and biodynamic modeling yield insights into detoxification mechanisms in the mayfly Neocloeon triangulifer

Diversity and biomass of aquatic insects decline in metal-rich aquatic environments, but the mechanisms by which insects from such environments cope with potentially toxic metal concentrations to survive through adulthood are less well understood. In this study, we measured Zn concentrations and isotopes in laboratory-reared diatoms and mayflies ( Neocloeon triangulifer ) from larval through adult stages. The larvae were fed Zn-enriched diatoms, and bio-concentrated Zn by a factor of 2.5–5 relative to the diatoms but maintained the same Zn-isotopic ratio. These results reflect the importance of dietary uptake and the greater rate of uptake relative to excretion or growth. Upon metamorphosis to subimago, Zn concentrations declined by > 70%, but isotopically heavy Zn remained in the subimago bodies. We surmised that the loss of isotopically light Zn during metamorphosis was due to the loss of detoxified Zn and retention of metabolically useful Zn. Through the transition from subimago to imago, Zn concentrations and isotope ratios were virtually unchanged. Because the decrease in Zn body concentration and increase in heavier Zn are seen in the subimagos relative to the larvae, the compartmentalization of Zn must be occurring within the larvae. A biodynamic model was constructed, allowing for isotopic fractionation and partitioning of Zn between metabolically essential and detoxified Zn reservoirs within larvae. The model provides a consistent set of rate and fractionation constants that successfully describe the experimental observations. Specifically, metabolically essential Zn is isotopically heavier and is tightly held once assimilated, and excess, isotopically light Zn is sequestered, detoxified, and ultimately lost during the metamorphosis of larvae to subimagos. To our knowledge, this is the first documentation of in vivo isotopic fractionation in insects, offering an improved understanding of the mechanisms and rates by which the N. triangulifer larvae regulate excess Zn in their bodies.

Science of the Total Environment↗

USGS2016

The role of natural biogeochemical barriers in limiting metal loading to a stream affected by mine drainage

Rio San Giorgio (Iglesiente, Sardinia, Italy), a stream affected by abandoned mine wastes, is characterized by dense vegetation in the streambed, mainly comprised of Phragmites australis and Juncus acutus . This vegetation creates natural biogeochemical barriers that drive mineralization processes and attenuate metals load in the stream. Several techniques, covering scales from micrometres to kilometres, were applied to investigate the biogeochemical processes: water chemistry, injected hydrologic tracer, mineralogy, microscopic investigation and X-ray spectroscopy. From this multiscale and multimethod approach, we recognized two predominant sets of biogeochemical processes: microbially driven metal sulphide precipitation, mainly resulting in pyrite formation; and plant uptake of metals that leads to formation of iron oxide-hydroxide and incorporation of Zn within the roots and aerial part (stem and leaves). The dense vegetation in the Rio San Giorgio streambed controls its morphology, velocity of streamflow, and, as reflected by observed bromide-tracer loss, enhanced water exchange between the streambed and the hyporheic zone. The combined effect of these vegetative controls is to establish biogeochemical barriers that greatly retard trace-metal mobility in the hyporheic zone. We estimated this effect can lead to an apparent decrease in Zn load up to 60%.

Iglesias↗

USGS2016

Contrasting distributions of groundwater arsenic and uranium in the western Hetao basin, Inner Mongolia: Implication for origins and fate controls

Although As concentrations have been investigated in shallow groundwater from the Hetao basin, China, less is known about U and As distributions in deep groundwater, which would help to better understand their origins and fate controls. Two hundred and ninety-nine groundwater samples, 122 sediment samples, and 14 rock samples were taken from the northwest portion of the Hetao basin, and analyzed for geochemical parameters. Results showed contrasting distributions of groundwater U and As, with high U and low As concentrations in the alluvial fans along the basin margins, and low U and high As concentrations downgradient in the flat plain. The probable sources of both As and U in groundwater were ultimately traced to the bedrocks in the local mountains (the Langshan Mountains). Chemical weathering of U-bearing rocks (schist, phyllite, and carbonate veins) released and mobilized U as UO 2 (CO 3 ) 2 2 − and UO 2 (CO 3 ) 3 4 − species in the alluvial fans under oxic conditions and suboxic conditions where reductions of Mn and NO 3 − were favorable (OSO), resulting in high groundwater U concentrations. Conversely, the recent weathering of As-bearing rocks (schist, phyllite, and sulfides) led to the formation of As-bearing Fe(III) (hydr)oxides in sediments, resulting in low groundwater As concentrations. Arsenic mobilization and U immobilization occurred in suboxic conditions where reduction of Fe(III) oxides was favorable and reducing conditions (SOR). Reduction of As-bearing Fe(III) (hydr)oxides, which were formed during palaeo-weathering and transported and deposited as Quaternary aquifer sediments, was believed to release As into groundwater. Reduction of U(VI) to U(IV) would lead to the formation of uraninite, and therefore remove U from groundwater. We conclude that the contrasting distributions of groundwater As and U present a challenge to ensuring safe drinking water in analogous areas, especially with high background values of U and As.

Hetao Basin, Inner Mongolia↗

USGS2015

Aquatic pollution increases use of terrestrial prey subsidies by stream fish

Stream food webs are connected with their riparian zones through cross-ecosystem movements of energy and nutrients. The use and impact of terrestrial subsidies on aquatic consumers is determined in part by in situ biomass of aquatic prey. Thus, stressors such as aquatic pollutants that greatly reduce aquatic secondary production could increase the need for and reliance of stream consumers on terrestrial resource subsidies. To test this hypothesis, we surveyed stream fish, their diets and resource availability in 16 subalpine streams over a regional gradient of trace metals known to strongly impact aquatic insect communities (i.e. fish prey) in the Colorado Rocky Mountains, USA. Fish increased their reliance on terrestrial insect prey as stream metals increased. Relative biomass of terrestrial insects in stomach contents of Brook and Brown Trout increased with respect to aquatic insect biomass and total stomach contents. Drifting insect biomass showed a declining trend for aquatic, but not terrestrial insects, over the metal gradient. Trout densities were unrelated to metal concentrations in streams where we found fish. Synthesis and applications . Our results indicate that diets of aquatic consumers can become more terrestrial as aquatic stressors that limit in situ food production increase and that these subsidies may compensate for loss of aquatic resources. This work implies an important connection between preserving aquatic–terrestrial linkages and management of fish populations in stressed watersheds. Specifically, intact riparian zones and aquatic–terrestrial linkages are likely to be important for maintaining trout production in streams with moderate metal contamination.

Colorado↗

USGS2015

Environmental effects on the aquatic system and metal discharge to the Mediterranean Sea from a near-neutral zinc-ferrous sulfate mine drainage

After mine closure in the 1980s and subsequent shutdown of the dewatering system, groundwater rebound led to drainage outflow from the Casargiu gallery (Montevecchio mine, SW Sardinia, Italy) beginning in 1997. Mine drainage had pH 6.0 and dissolved concentrations of sulfate (5000 mg/L) and metals (e.g., 1000 mg/L Zn, 230 mg/L Fe, 150 mg/L Mn) much higher than those previously measured in groundwater under dewatering conditions. As compared with the first stages of rebound at Casargiu, a very high contamination level still persists after more than 15 years of flushing. Mine drainage (20–70 L/s; pH 6.0 ± 0.2; Zn-Mg-Ca-SO 4 composition) flowed into the Rio Irvi. Abundant precipitation of amorphous Fe(III)-(oxy)hydroxides occurred. Moreover, sulfate-bearing green rust was observed to flocculate in the reach of the Rio Irvi where pH was still circumneutral. Water sampling along this stream for about 6 km almost to its mouth in the Mediterranean Sea showed a pH decrease from 6.0 to 4.0 and a significant removal of Fe (46 %) and As (96 %), while sulfate, Zn, Mn, Co, Ni, and Cd showed small variations downstream. Lead was initially adsorbed onto Fe(III)-(oxy)hydroxides, then desorbed as pH dropped below 5. The estimated amount of dissolved metals discharged into the Mediterranean Sea is significant (e.g., 900 kg/day Zn, 1.4 kg/day Cd, 5 kg/day Ni). In particular, a conservative estimation of the amount of Zn discharged to the sea is about 330 ton/year, which would correspond to 1.4 % of the global annual flux of dissolved Zn from uncontaminated rivers to the oceans.

Sardinia↗

USGS2015

Isotopic insights into biological regulation of zinc in contaminated systems

Aquatic organisms use a variety of biogeochemical reactions to regulate essential and non-essential trace metals. Many of these mechanisms can lead to isotopic fractionation, thus measurement of metal isotopes may yield insights into the processes by which organisms respond to metal exposure. We illustrate these concepts with two case studies, one involving an intra- and the other an extra-cellular mechanism of Zn sequestration. In the first study, the mayfly Neocloeon triangulifer was grown in the laboratory, and fed a diet of Zn-doped diatoms at Zn levels exceeding the requirements for normal mayfly life functions. The N. triangulifer larvae consumed the diatoms and retained their Zn isotopic signature. Upon metamorphosis, the subimago life stage lost Zn mass either in the exuvia or by excretion, and the Zn retained was isotopically enriched. Thus, Zn uptake is nonfractionating, but Zn regulation favors the lighter isotope. Thus the Zn remaining in the subimago was isotopically heavier. In the second study, Zn was adsorbed on the cell walls and exopolysaccharide secretions of cyanobacteria, which favored the heavier Zn isotope. Continued adsorption eventually resulted in nucleation and biomineralization of hydrozincite {Zn5(CO3)2(OH)6}. These case studies demonstrate the utility of Zn isotopes to provide insights into how aquatic insects respond to metal exposure.

Procedia Earth and Planetary Science↗

USGS2014

Quantifying biomineralization of zinc in the Rio Naracauli (Sardinia, Italy), using a tracer injection and synoptic sampling

Streams draining mined areas throughout the world commonly have high concentrations of Zn. Because Zn is not easily removed from stream water and because it can be toxic to aquatic organisms, its presence is a persistent problem. The discovery of biomineralization of Zn-bearing solids in the mine drainage of Rio Naracauli, in Sardinia, Italy, provides insights into strategies for removing Zn and improving water quality in streams affected by mine drainage. Until now, the transport and attenuation of Zn has not been quantified in this stream setting. A continuous tracer injection experiment was conducted to quantify the biomineralization process and to identify the loading of constituents that causes a change from precipitation of hydrozincite [Zn 5 (CO 3 ) 2 (OH) 6 ] in the upstream reach to precipitation of a Zn-silicate phase downstream. Based on the mass-load calculations derived from the tracer experiment, about 1.2 kg/day of Zn is sequestered in hydrozincite. This biomineralization represents nearly 90% removal of Zn. Other elements such as Pb and Cd also are sequestered, either in the hydrozincite, or in a separate phase that forms simultaneously. In the lower 600 m of the stream, where the Zn-silicate forms, as much as 0.7 kg/day Zn are sequestered in this solid, but additions of Zn to the stream from groundwater discharge lead to an overall increase in load in that portion of the Rio Naracauli.

Sardinia↗