Application of environmental groundwater tracers at the Sulphur Bank Mercury Mine, California, USA

Boron, chloride, sulfate, δD, δ¹⁸O, and ³H concentrations in surface water and groundwater samples from the Sulphur Bank Mercury Mine (SBMM), California, USA were used to examine geochemical processes and provide constraints on evaporation and groundwater flow. SBMM is an abandoned sulfur and mercury mine with an underlying hydrothermal system, adjacent to Clear Lake, California. Results for non-³H tracers (i.e., boron, chloride, sulfate, δD, and δ¹⁸O) identify contributions from six water types at SBMM. Processes including evaporation, mixing, hydrothermal water input and possible isotopic exchange with hydrothermal gases are also discerned. Tritium data indicate that hydrothermal waters and other deep groundwaters are likely pre-bomb (before ~1952) in age while most other waters were recharged after ~1990. A boron-based steady-state reservoir model of the Herman Impoundment pit lake indicates that 71–79% of its input is from meteoric water with the remainder from hydrothermal contributions. Results for groundwater samples from six shallow wells over a 6–month period for δD and δ¹⁸O suggests that water from Herman Impoundment is diluted another 3% to more than 40% by infiltrating meteoric water, as it leaves the site. Results for this investigation show that environmental tracers are an effective tool to understand the SBMM hydrogeologic regime.

---

Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.

---

Résumé Les concentrations en bore, chlorure, sulfate, δD, δ¹⁸O, et ³H d’échantillons d’eaux de surface et souterraine prélevés dans le banc de soufre de la mine de mercure (SBMM en anglais) en Californie, USA, ont été utilisées pour étudier les processus géochimiques et pour fournir des contraintes à l’évaporation et à l’écoulement des eaux souterraines. La SBMM est une mine de soufre et de mercure abandonnée, adjacente au lac Clear en Californie et sous laquelle se trouve un système hydrothermal.Les résultats des traceurs autres que le tritium (bore, chlorure, sulfate, δD, et δ¹⁸O) ont permis d’identifier des contributions de six types d’eaux à SBMM. Des processus tels que l’évaporation, le mélange, l’entrée d’eau hydrothermale et de possibles échanges isotopiques avec des gaz hydrothermaux ont également été identifiés. Les données de tritium montrent que les eaux hydrothermales et d’autres eaux profondes sont probablement d’age antérieure à la bombe (avant ~1952), alors que la plupart des autres eaux sont issues de la recharge après ~1990. Un modèle de réservoir représentant le lac situé dans la partie Herman Impoundment de l’ancienne mine, en régime permanent et basé sur le bore, montre que 71–79% de l’eau provient des précipitations, le reste provenant de contributions hydrothermales. Les résultats de δD et δ¹⁸O pour des échantillons d’eau souterraine de six puits peu profonds sur une période de 6 mois suggèrent que l’eau de Hermann Impoundment est encore diluée entre 3% jusqu’à plus de 40% lorsqu’elle quitte le site du fait de l’infiltration d’eau météorique. Les résultats de cette étude montrent que les traceurs environnementaux constituent un outil efficace pour comprendre le régime hydrogéologique de la SBMM.

---

Resumen Se han utilizado datos de concentraciones de boro, cloruros, sulfatos, δD, δ¹⁸O, y ³H en muestras de aguas superficiales y subterráneas procedentes de la Mina de Mercurio Sulphur Bank (SBMM), California, USA, para estudiar los procesos geoquímicos y caracterizar la evaporación y el flujo del agua subterránea. SBMM es una mina abandonada de azufre y mercurio con un sistema hidrotermal subyacente, cercano al Lago Clear, California.Los resultados de los trazadores que no son ³H (por ejemplo, boro, cloruros, sulfatos δD, y δ¹⁸O) identifican las contribuciones de seis tipos de agua en la SBMM. Se han identificado diversos procesos, como evaporación, mezcla, entrada de agua hidrotermal y la posibilidad de intercambios isotópicos con gases hidrotermales. Los datos de tritio indican que las aguas hidrotermales y otras aguas subterráneas profundas son probablemente pre-bombas (previas a ~1952) en edad mientras que la mayoría de las otras aguas se han recargado después de ~1990. Un modelo estacionario basado en el boro de la fosa del lago Herman Impoundment indica que el 71–79% de su entrada procede de agua meteórica con restos de contribución hidrotermal. Los resultados para las muestras de aguas subterráneas procedentes de seis pozos superficiales en un periodo de 6 meses para δD y δ¹⁸O sugieren que el agua procedente de Herman Impoundment se diluye en otro 3% hasta más del 40% debido a la infiltración de agua meteórica., que sale del sitio. Los resultados de esta investigación muestran que los trazadores ambientales son una herramienta efectiva para entender el régimen hidrogeológico de la SBMM.

     

Particulate content of savanna fire emissions

As part of the FOS-DECAFE experiment at Lamto (Ivory Coast) in January 1991, various aerosol samples were collected at ground level near prescribed fires or under local background conditions, to characterize the emissions of particulate matter from the burning of savanna vegetation. This paper deals with total aerosol (TPM) and carbon measurements. Detailed trace element and polycyclic hydrocarbon data are discussed in other papers presented in this issue.Near the fire plumes, the aerosols from biomass burning are primarily of a carbonaceous nature (C%70% of the aerosol mass) and consist predominantly of submicron particles (more than 90% in mass.) They are characterized by their organic nature (black to total carbon ratio Cb/Ct in the range 3–20%) and their high potassium content (K/Cb0.6). These aerosols undergo aging during their first minutes in the atmosphere causing slight alterations in their size distribution and chemical composition. However, they remain enriched in potassium (K/Cb=0.21) and pyrene, a polycyclic aromatic hydrocarbon, such that both of these species may be used as tracers of savanna burning aerosols. We show that during this period of the year, the background atmosphere experiences severe pollution from both terrigenous sources and regional biomass burning (44% of the aerosol). Daynight variations of the background carbon concentrations suggest that fire ignition and spreading occur primarily during the day. Simultaneous TPM and CO₂ real-time measurements point to a temporal and spatial heterogeneity of the burning so that the ratio of the above background concentrations (TPM/CO₂) varies from 2 to 400 g/kg C. Smoldering processes are intense sources of particles but particulate emissions may also be important during the rapidly spreading heading fires in connection with the generation of heavy brown smoke. We propose emission factor values (EF) for aerosols from the savanna biomass burning aerosols: EF (TPM)=11.4±4.6 and 69±25 g/kg C_{dry plant} and EF(Ct)=7.4±3.4 and 56±16 g C/kg C_{dry plant} for flaming and smoldering processes respectively. In these estimates, the range of uncertainty is mostly due to the intra-fire variability. These values are significantly lower than those reported in the literature for the combustion of other types of vegetation. But due to the large amounts of vegetation biomass being burnt in African savannas, the annual flux of particulate carbon into the atmosphere is estimated to be of the order of 8 Tg C, which rivals particulate carbon emissions from anthropogenic activities in temperate regions.     

An ephemeral turbidity maximum generated by resuspension of organic-rich matter in a macrotidal estuary, S.W. Wales

An ephemeral estuarine turbidity maximum (ETM) occurs at high water in the macrotidal Taf estuary (SW Wales, United Kingdom). A new mechanism of ETM formation, due to resuspension and advection of material by flood tidal currents, is observed that differs from classical mechanisms of gravitational circulation and tidal pumping. The flood tide advances across intertidal sand flats in the main body of the estuary, progressively entraining material from the rippled sands. Resuspension creates, a turbid front that has suspended sediment concentrations (SSC) of about 4,000 mg I⁻¹ by the time it reaches its landward limit which is also the landward limit of salt penetration. This turbid body constitutes the ETM. Deposition occurs at high slack water but the ETM retains SSC values up to 800 mg I⁻¹, 1–2 orders of magnitude greater than ambient SSC values in the river and estuarine waters on either side. The ETM retreats down the estuary during the ebb; some material is deposited thinly across emergent intertidal flats and some is flushed out of the estuary. A new ETM is generated by the next flood tide. Both location and SSC of the ETM scale on Q/R³ where Q is tidal range and R is river discharge. The greatest expression of the ETM occurs when a spring tide coincides with low river discharge. It does not form during high river discharge conditions and is poorly developed on neap tides. Particles in the ETM have effective densities (120–160 kg m⁻³) that are 3–4 times less than those in the main part of the estuary at high water. High chlorophyll concentrations in the ETM suggest that flocs probably originate from biological production in the estuary, including production on the intertidal sand flats.     

Lake Sediment Core Records of Sulphur Accumulation and Sulphur Isotopic Composition in Central Ontario, Canada Lakes

Stable isotopic compositions and concentrations of total sedimentary sulphur (S) were determined in cores from 6 lakes in the acid-sensitive Muskoka-Haliburton region of south-central Ontario. The isotopic composition of S in deep sediment (> ~ 20 cm) was approximately constant in all lakes, and indicated a pre-industrial δ ³⁴S value between +4.0 and +5.3‰, which is similar to current bulk deposition. Similarly, total S concentrations in deep sediment were relatively low (1.9–5 mg S g⁻¹ dwt) and approximately constant with depth within cores. All lakes exhibited up-core increases in total S and decreases in δ ³⁴S at a depth corresponding to the beginning of industrialization in the Great Lakes region ( ~ 1900), resulting in a generally reciprocal depth pattern between total S concentration and δ ³⁴S ratios. While initial shifts in total S and δ ³⁴S were likely due to enhanced SO₄ reduction of newly available anthropogenic SO₄, both the magnitude and pattern of up-core S enrichment and shifts in δ ³⁴S varied greatly among lakes, and did not match changes in S deposition post 1900. Differences between lakes in total S and δ ³⁴S were not related to any single hydrologic (e.g., residence time) or physical (e.g., catchment-area-to-lake area ratio) lake characteristic. This work indicates that sediment cores do not provide consistent records of changes in post-industrial S deposition in this region, likely due to redox-related mobility of S in upper sediment.     

3D numerical modelling of fluid flow in the Val-d’Or orogenic gold district: major crustal shear zones drain fluids from overpressured vein fields

Fluid flow patterns have been determined using oxygen isotope isopleths in the Val-d’Or orogenic gold district. 3D numerical modelling of fluid flow and oxygen isotope exchange in the vein field shows that the fluid flow patterns can be reproduced if the lower boundary of the model is permeable, which represents middle or lower crustal rocks that are infiltrated by a metamorphic fluid generated at deeper levels. This boundary condition implies that the major crustal faults so conspicuous in vein fields do not act as the only major channel for upward fluid flow. The upper model boundary is impermeable except along the trace of major crustal faults where fluids are allowed to drain out of the vein field. This upper impermeable boundary condition represents a low-permeability layer in the crust that separates the overpressured fluid from the overlying hydrostatic fluid pressure regime. We propose that the role of major crustal faults in overpressured vein fields, independent of tectonic setting, is to drain hydrothermal fluids out of the vein field along a breach across an impermeable layer higher in the crust and above the vein field. This breach is crucial to allow flow out of the vein field and accumulation of metals in the fractures, and this breach has major implications for exploration for mineral resources. We propose that tectonic events that cause episodic metamorphic dehydration create a short-lived pulse of metamorphic fluid to rise along zones of transient permeability. This results in a fluid wave that propagates upward carrying metals to the mineralized area. Earthquakes along crustal shear zones cause dilation near jogs that draw fluids and deposit metals in an interconnected network of subsidiary shear zones. Fluid flow is arrested by an impermeable barrier separating the hydrostatic and lithostatic fluid pressure regimes. Fluids flow through the evolving and interconnected network of shear zones and by advection through the rock matrix. Episodic breaches in the impermeable barrier along the crustal shear zones allow fluid flow out of the vein field.     

Celestite formation, bacterial sulphate reduction and carbonate cementation of Eocene reefs and basinal sediments (Igualada, NE Spain)

Petrographic and geochemical studies of an Upper Eocene reef and associated basinal sediments from the mixed carbonate–siliciclastic fill of the south‐eastern Pyrenean foreland basin near Igualada (NE Spain) provide new insights into the evolution of subsurface hydrology during the restriction of a marine basin. The reef deposits are located on delta‐lobe sandstones and prodelta marls, which are overlain by hypersaline carbonates and Upper Eocene evaporites. Authigenic celestite (SrSO₄) is an important component in the observed diagenetic sequences. Celestite is a significant palaeohydrological indicator because its low solubility constrains transportation of Sr²⁺ and SO₄^2? in the same diagenetic fluid. Stable isotopic analyses of carbonates in the reef indicate that meteoric recharge was responsible for aragonite stabilization and calcite cementation. Sulphur and oxygen isotope geochemistry of the celestite demonstrates that it formed from residual sulphate after bacterial sulphate reduction, but also requires that there was a prior episode of sulphate recycling. Meteoric water reaching the reef and basinal areas was most probably charged with SO₄^2? from the dissolution of younger Upper Eocene marine evaporites. This sulphate, combined with organic matter present in the sediments, fuelled bacterial sulphate reduction in the meteoric palaeoaquifer. Strontium for celestite precipitation was partly derived in situ from dissolution of aragonite corals in the reef and basinal counterparts. However, ⁸⁷Sr/⁸⁶Sr data also suggest that Sr²⁺ was partly derived from dissolution of overlying evaporites. Mixing of these two fluids promoted celestite formation. The carbonate stable isotopic data suggest that the local meteoric water was enriched in ¹⁸O compared with that responsible for stabilization of other reefs along the basin margin. Furthermore, meteoric recharge at Igualada post‐dated evaporite deposition in the basin, whereas other parts of the same reef complex were stabilized before evaporite formation. This discrepancy resulted from the spatial distribution of continental siliciclastic units that acted as groundwater conduits.     

Toxic Cyanobacteria in Greek Freshwaters, 1987—2000: Occurrence,Toxicity, and Impacts in the Mediterranean Region

In a survey in Greece from 1987 to 2000 hepatotoxic cyanobacterial blooms were observed in 9 out of 33 freshwaters. Microcystins (MCYSTs) were detected by HPLC in 7 of these lakes, and the total MCYST concentration per scum dry weight ranged from 50.3 to 1638 ± 464 μg g^—1. Cyanobacterial genera (Microcystis, Anabaena, Anabaenopsis, Aphanizomenon, Cylindrospermopsis) with known toxin producing taxa were present in 31 freshwaters. From our data and a review of the literature, it would appear that Mediterranean countries are more likely 1) to have toxic cyanobacterial blooms consisting of Microcystis spp. and 2) to have higher intracellular MCYST concentrations. A case study in Lake Kastoria is used to highlight seasonal patterns of cyanobacterial and MCYST‐LR occurrence and to assess cyanotoxin risk. Cyanobacterial biovolume was high (> 11 μL L^—1) throughout the year and was in excess of Guidance Level 2 (10 μL L^—1) proposed by WHO for recreational waters and Alert Level 2 for drinking water. Further, surface water samples from April to November exceeded Guidance Level 3, with the potential for acute cyanobacterial poisoning. Intracellular MCYST‐LR concentrations (max 3186 μg L^—1) exceeded the WHO guideline for drinking water (1 μg L^—1) from September to November with a high risk of adverse health effects. Preliminary evidence indicates that in 3 lakes microcystins are accumulated in some aquatic organisms. Generally, a high risk level can be deduced from the data for the Mediterranean region.     

Modeling Spatially and Temporally Complex Land‐Cover Change: The Case of Western Honduras*

This article presents an econometric analysis of land‐cover change in western Honduras. Ground‐truthed satellite image analysis indicates that between 1987 and 1996 net reforestation occurred in the 1,015‐km² study region. While some reforestation can be attributed to a 1987 ban on logging, the area of reforestation greatly exceeds that of previously clear‐cut areas. Further, new area was also deforested between 1987 and 1996. Thus, the observed land‐cover changes represent a complex mosaic of changing land‐use patterns across time and space. The analysis contributes to the literature on land‐cover change modeling in that: (1) it compares two econometric approaches to capture complex and often bidirectional changes in land cover from 1987 to 1996 as a function of agricultural suitability and transportation costs, and (2) it addresses techniques to identify and correct for spatial autocorrelation in a categorical regression framework.     

The Elusive AD 1826 Tsunami, South Westland, New Zealand

In AD 1826 sealers reported earthquake and tsunami activity in Fiordland, although, contemporary or near‐contemporary accounts of tsunami inundation at the time are elusive. A detailed analysis of recent sediments from Okarito Lagoon builds on contextual evidence provided by earlier research concerning past tsunami inundation. Sedimentological, geochemical, micropalaeontological and geochronological data are used to determine palaeoenvironments before, during and after what was most probably tsunami inundation in AD 1826. The most compelling chronological control is provided fry a young cohort of trees growing on a raised shoreline bench stranded fry a drop in the lagoon water level following tsunami inundation.