Applied Geochemistry (v.25, #5)

Groundwater residence time and movement in the Maltese islands – A geochemical approach by M.E. Stuart; L. Maurice; T.H.E. Heaton; M. Sapiano; M. Micallef Sultana; D.C. Gooddy; P.J. Chilton (609-620).
The Maltese islands are composed of two limestone aquifers, the Upper and Lower Coralline Limestone separated by an aquitard, the ‘Blue Clay’. The Lower Coralline Limestone is overlain in part by the poorly permeable Globigerina Limestone. The upper perched aquifers are discontinuous and have very limited saturated thickness and a short water level response time to rainfall. Frequent detections of coliforms suggest a rapid route to groundwater. However, the unsaturated zone has a considerable thickness in places and the primary porosity of the Upper Coralline Limestone is high, so there is likely to be older recharge by slow matrix flow as well as rapid recharge from fractures. Measurement of SF6 from a pumping station in a deep part of one of the perched aquifers indicated a mean saturated zone age of about 15 a. The Main Sea Level aquifers (MSL) on both Malta and Gozo have a large unsaturated thickness as water levels are close to sea level. On Malta, parts of the aquifer are capped by the perched aquifers and more extensively by the Globigerina Limestone. The limited detection of coliform bacteria suggests only some rapid recharge from the surface via fractures or karst features. Transmissivity is low and 3H and CFC/SF6 data indicate that saturated zone travel times are in the range 15–40 a. On Gozo the aquifer is similar but is more-extensively capped by impermeable Blue Clay. CFC data show the saturated zone travel time is from 25 a to possibly more than 60 a. Groundwater age is clearly related to the extent of low-permeability cover. The δ 13C signature of groundwater is related to the geochemical processes which occur along the flowpath and is consistent with residence time ages in the sequence; perched aquifers < Malta MSL < Gozo MSL. The 18O and 2H enriched isotopic signature of post 1983 desalinated water can be seen in more-modern groundwater, particularly the urbanized areas of the perched and Malta MSL aquifers. In all aquifers, movement of solutes from the surface travelling slowly through the matrix provide a long-term source of groundwater contaminants such as NO3.

Recent geochemical studies provide evidence that changes in vertical distributions of nutrients in lake sediments are driven by anthropogenic activities, based primarily on trends of increasing concentrations in upper sediment layers. However, the present study shows that vertical concentration profiles of C, N and P in lake sediments can be higher in the upper, most recently deposited sediment strata, driven largely by natural diagenetic processes and not eutrophication alone. Sediment cores from 14 different lakes in New Zealand and China were examined ranging from oligotrophic to highly eutrophic and shallow to deep, and it was found that the shape of vertical profiles of total P, a key nutrient for lake productivity, can be similar in sediments across gradients of widely differing trophic status. Empirical and mechanistic diagenesis steady state profile models were derived and applied to describe the vertical distribution of C, N and P in the sediments. These models, which focus on large scale temporal (decades) and spatial (up to 35 cm in the vertical) processes, revealed that density-differentiated burial and biodiffusive mixing, were strongly correlated with vertical concentration gradients of sediment C, N and P content, whereas lake trophic status was not. A sensitivity analysis of parameters included in the diagenetic model further showed that the processes including flux of organic matter to the sediment–water interface, burial (net sedimentation), breakdown of organic matter and biodiffusion all can significantly influence the vertical distribution of sediment P content. It was concluded that geochemical studies attempting to evaluate drivers of the vertical distribution of sediment C, N and P content in lake sediments should also account for the natural diagenetic drivers of vertical concentration gradients, assisted with application of similar models to those presented in this study. This would include quantification of key sediment diagenesis model parameters to separate out the influence of anthropogenic activities.

Fractionation, distribution and transport of mercury in rivers and tributaries around Wanshan Hg mining district, Guizhou province, southwestern China: Part 1 – Total mercury by Hua Zhang; Xinbin Feng; Thorjørn Larssen; Lihai Shang; Rolf D. Vogt; Sarah E. Rothenberg; Ping Li; Hui Zhang; Yan Lin (633-641).
The Wanshan Hg mining area in Guizhou, China, was one of the world’s largest Hg producing regions. Numerous mine-waste and calcines still remain, leaching Hg to local rivers and streams and potentially impacting the local population. Several studies have been published on local environmental impacts of these mining and retorting residues, but a comprehensive, regional survey on the distribution of Hg in the rivers in the region, as presented in this paper, has not previously been conducted. This study focuses on the regional distribution and temporal variation of aqueous Hg fractions in the five main watercourses draining the Wanshan Hg mining and retorting area, covering more than 700 km2. Three sampling campaigns were carried out in 2007 and 2008, covering high flow, normal flow and low flow periods. Total (THg), particulate (PHg), dissolved (DHg) and reactive (RHg) Hg fractions were determined. All rivers had the highest Hg concentrations at sample sites about 100–500 m downstream of the mine wastes. Total Hg concentrations ranged from extremely high (up to 12,000 ng L−1) at the sample site just 100 m below mine wastes, to quite low in tributary streams (1.9 ng L−1, about 14 km downstream of the mine wastes). Total Hg and PHg concentrations were usually highest during high flow periods in the Hg-contaminated areas (i.e. THg ⩾ 50 ng L−1), while in the less-impacted downstream areas (with THg < 50 ng L−1) the Hg concentrations were usually lowest during high flow periods. Although highly elevated concentrations of Hg in water samples were found just downstream of the mine wastes, the concentrations decreased sharply to well below 50 ng L−1 (US EPA Hg concentration standard for protection of fresh water), within only 6–8 km downstream. Concentrations of THg were highly dominated by and correlated with PHg (R 2  = 0.996–0.999, P  < 0.001); PHg constituted more than 80% of THg in Hg-contaminated areas, and could account for 99.6% of the THg close to the mine wastes.

Water samples were collected during normal flow (2007) and during a drought period (2008) from five rivers and tributaries draining the Wanshan Hg mining district, Guizhou, China. Unfiltered methylmercury (MeHg) as well as particulate and dissolved fractions of MeHg (P-MeHg, D-MeHg) were measured to assess the spatial and temporal variation of MeHg contamination in the local river system. Most locations (about 80%) displayed higher MeHg concentrations during drought period than during normal discharge conditions. Concentrations of MeHg during the drought period ranged from <0.035 to 11 ng L−1 (geometric mean: 0.43), while during normal flow the concentrations ranged from <0.035 to only 3.4 ng L−1 (geometric mean: 0.21). Concentrations of MeHg were positively correlated with total Hg (THg) concentrations (R 2  = 0.20–0.58, P  < 0.001) and inversely related to distance from the calcines, during both sampling periods (R 2  = 0.34 and 0.23, P  < 0.001, for low and normal flow, respectively) indicating that calcines may be important sources of MeHg to the downstream environment. Approximately 39% of MeHg was bound to particulates and the rest was transported in the dissolved phase along stretches of the entire river, which was different from THg, as this was mainly transported bound to particulates (commonly more than 80%).

Trace metal cycling in natural waters is highly influenced by the amount and type of dissolved organic C (DOC). Although determining individual species of DOC is unrealistic, there has been success in classifying DOC by determining operationally defined fractions. However, current fractionation schemes do not allow for the simultaneous quantification of associated trace metals. Using operational classifications, a scheme was developed to fractionate DOC based on a set of seven solid-phase extraction (SPE) cartridges. The cartridges isolated fractions based on a range of specific mechanisms thought to be responsible for DOC aggregation in solution, as well as molecular weight. The method was evaluated to determine if it can identify differences in DOC characteristics, including differences in Cu–DOC complexation. Results are that: (1) cartridge blanks were low for both DOC and Cu, (2) differences are observed in the distribution of DOC amongst the fractions from various sources that are consistent with what is known about the DOC materials and the mechanisms operative for each cartridge, (3) when present as a free cation, Cu was not retained by non-cationic cartridges allowing the method to be used to assess Cu binding, (4) the capability of the method to provide quantitative assessment of Cu–DOC complexation was demonstrated for a variety of DOC standards, (5) Cu was found to preferentially bind with high molecular weight fractions of DOC, and (6) estimated partitioning coefficients and conditional binding constants for Cu were similar to those reported elsewhere. The method developed describes DOC characteristics based on specific bonding mechanisms (hydrogen, donor–acceptor, London dispersion, and ionic bonding) while simultaneously quantifying Cu–DOC complexation. The method provides researchers a means of describing not only the extent of DOC complexation but also how that complex will be behave in natural waters.

Using chloride and other ions to trace sewage and road salt in the Illinois Waterway by Walton R. Kelly; Samuel V. Panno; Keith C. Hackley; Hue-Hwa Hwang; Adam T. Martinsek; Momcilo Markus (661-673).
Chloride concentrations in waterways of northern USA are increasing at alarming rates and road salt is commonly assumed to be the cause. However, there are additional sources of Cl in metropolitan areas, such as treated wastewater (TWW) and water conditioning salts, which may be contributing to Cl loads entering surface waters. In this study, the potential sources of Cl and Cl loads in the Illinois River Basin from the Chicago area to the Illinois River’s confluence with the Mississippi River were investigated using halide data in stream samples and published Cl and river discharge data. The investigation showed that road salt runoff and TWW from the Chicago region dominate Cl loads in the Illinois Waterway, defined as the navigable sections of the Illinois River and two major tributaries in the Chicago region. Treated wastewater discharges at a relatively constant rate throughout the year and is the primary source of Cl and other elements such as F and B. Chloride loads are highest in the winter and early spring as a result of road salt runoff which can increase Cl concentrations by up to several hundred mg/L. Chloride concentrations decrease downstream in the Illinois Waterway due to dilution, but are always elevated relative to tributaries downriver from Chicago. The TWW component is especially noticeable downstream under low discharge conditions during summer and early autumn when surface drainage is at a minimum and agricultural drain tiles are not flowing.Increases in population, urban and residential areas, and roadways in the Chicago area have caused an increase in the flux of Cl from both road salt and TWW. Chloride concentrations have been increasing in the Illinois Waterway since around 1960 at a rate of about 1 mg/L/a. The increase is largest in the winter months due to road salt runoff. Shallow groundwater Cl concentrations are also increasing, potentially producing higher base flow concentrations. Projected increases in population and urbanization over the next several decades suggest that the trend of increasing Cl concentrations and loads will continue. Given the susceptibility of aquatic ecosystems to increasing Cl concentrations, especially short-term spikes following snow melts, deleterious effects on riverine ecosystems would be expected.

Solubility experiments were performed on nanocrystalline scorodite and amorphous ferric arsenate. Nanocrystalline scorodite occurs as stubby prismatic crystals measuring about 50 nm and having a specific surface area of 39.88 ± 0.07 m2/g whereas ferric arsenate is amorphous and occurs as aggregated clusters measuring about 50–100 nm with a specific surface area of 17.95 ± 0.19 m2/g. Similar to its crystalline counterpart, nanocrystalline scorodite has a solubility of about 0.25 mg/L at around pH 3–4 but has increased solubilities at low and high pH (i.e. <2 and >6). Nanocrystalline scorodite dissolves incongruently at about pH > 2.5 whereas ferric arsenate dissolution is incongruent at all the pH ranges tested (pH 2–5). It appears that the solubility of scorodite is not influenced by particle size. The dissolution rate of nanocrystalline scorodite is 2.64 × 10−10  mol m−2  s−1 at pH 1 and 3.25 × 10−11  mol m−2  s−1 at pH 2. These rates are 3–4 orders of magnitude slower than the oxidative dissolution of pyrite and 5 orders of magnitude slower than that of arsenopyrite. Ferric arsenate dissolution rates range from 6.14 × 10−9  mol m−2  s−1 at pH 2 to 1.66 × 10−9  mol m−2  s−1 at pH 5. Among the common As minerals, scorodite has the lowest solubility and dissolution rate. Whereas ferric arsenate is not a suitable compound for As control in mine effluents, nanocrystalline scorodite that can be easily precipitated at ambient pressure and temperature conditions would be satisfactory in meeting the regulatory guidelines at pH 3–4.

Primary sink and source of geogenic arsenic in sedimentary aquifers in the southern Choushui River alluvial fan, Taiwan by Kuang-Liang Lu; Chen-Wuing Liu; Sheng-Wei Wang; Cheng-Shin Jang; Kao-Hung Lin; Vivian Hsiu-Chuan Liao; Chung-Min Liao; Fi-John Chang (684-695).
This work characterized the sink and source/mobility of As in the As-affected sedimentary aquifers of the southern Choushui River alluvial fan, central Taiwan. Major mineral phases and chemical components were determined by XRD and X-ray photoelectron spectroscopy (XPS). The partitioning of As and Fe among cores were determined by sequential extraction. Based on XPS results, the primary forms of Fe were hematite, goethite and magnetite. Sequential extraction data and the XRF analysis indicated that Fe oxyhydroxides and sulfides were likely to be the major sinks of As, particularly in the distal-fan. Furthermore, Fe oxyhydroxides retained higher As contents than As-bearing sulfides. The reductive dissolution of Fe oxyhydroxides, which accompanied high levels of HCO 3 - and NH 4 + concentrations, was likely the principal release mechanism of As into groundwater in this area. The dual roles of Fe oxyhydroxides which are governed by the local redox condition act as a sink and source in the aquifer. Ionic replacement by PO 4 3 - and HCO 3 - along with seasonal water table fluctuation, caused by monsoons and excessive pumping, contributed specific parts of As in the groundwater. The findings can be used to account for the inconsistency between Fe and As concentrations observed in groundwater.

To understand the effects of increased levels of CO2 on the marine realm, it is possible to study areas where, for natural reasons, there are emissions of CO2 from the seabed. One of these areas is located east of Panarea Island (Aeolian Islands – Southern Tyrrhenian Sea – Italy). Here, the volcanic activity that characterizes the Aeolian archipelago causes a continuous release of CO2 (up to 98% of the total gas) from several vents on the seafloor in shallow water. This area was studied by means of surface techniques and direct SCUBA diving surveys; the data presented refers to a field campaign performed in 2008. To collect the necessary data, some dedicated sampling and measuring techniques were developed for use in an underwater environment. The chemistry of the fluids and their influence on the water body was determined via logs and transects in the field and by gas-chromatographic and liquid-chromatographic laboratory analysis. The flux from some of the main gas vents was also measured directly underwater. Furthermore, some laboratory experiments in a two-layer stratified fluid were conducted to understand the main features of the physical interaction of a gas plume with the surrounding environment. Both field and laboratory experiments show that there is a development of a pseudo-convective cell around the rising plume with the formation of vortices that act as a physical barrier thus reducing the interaction between the plume and the surrounding water.

Dynamics of contaminants in phosphogypsum of the fertilizer industry of Huelva (SW Spain): From phosphate rock ore to the environment by Rafael Pérez-López; José Miguel Nieto; Israel López-Coto; Juan Luis Aguado; Juan Pedro Bolívar; María Santisteban (705-715).
The dynamics of trace elements from phosphate rock ore to the environment in a phosphoric acid plant located in SW Spain and the impact of phosphogypsum wastes were investigated through total digestion and BCR-sequential extraction. Based on total concentration, element transfer factors as criteria for examining the potential environmental risk of waste with respect to ore rock were calculated, and it was observed that most trace elements are only transferred into phosphogypsum at rates of 2–12%. However, based on those concentrations that are likely to be most readily mobile in the environment, phosphogypsum acts as a higher emission source of contaminants than the original rock. About 100 million tonnes of phosphogypsum are stack-piled in a dump of 1200 ha over salt-marshes of an estuary formed by the confluence of the Tinto and Odiel rivers. Phosphogypsum has been applied, at the recommended rate of 20–25 t/ha since 1978–2001, to improve fertility and reduce Na saturation in agricultural soils of the Guadalquivir river valley (140 km2). Phosphogypsum capacity as a source of mobile contaminants in three environmental scenarios (water leaching, exposure to oxidising and reducing conditions) was quantified by combining sequential extraction and waste mass. The amounts of mobile contaminants that could be released for every tonne of phosphogypsum are approximately 7 × 102  g Sr, 1.1 × 102  g Fe, 55 g Y, 30 g Ce, 12 g Cr, 11 g Ti, 5 g Zn, 4 g each of Cu and Pb, 3 g each of V and Cd, 2 g each of As and Ni and 1 g U. Multiplying these amounts by 100 Mt and 20–25 t/ha, it is possible to calculate risk assessments of phosphogypsum for both estuarine zones, e.g. in a hypothetical stack collapse and waste spilling, and agricultural soils, respectively.

Acid drainage at the inactive Santa Lucia mine, western Cuba: Natural attenuation of arsenic, barium and lead, and geochemical behavior of rare earth elements by Francisco Martín Romero; Rosa María Prol-Ledesma; Carles Canet; Laura Núñez Alvares; Ramón Pérez-Vázquez (716-727).
A detailed geochemical study was conducted at the inactive Zn–Pb mine of Santa Lucia, in western Cuba. The studied mine-wastes are characterized by high total concentrations of potentially toxic elements (PTE), with average values of 17.4% Fe, 5.47% Ba, 2.27% Pb, 0.83% Zn, 1724 mg/kg As and 811 mg/kg Cu. Oxidation of sulfide minerals in mine-waste dumps and in the open pit produces acid mine effluents (pH = 2.5–2.6) enriched in dissolved SO 4 2 - (up to 6754 mg/L), Fe (up to 4620 mg/L) and Zn (up to 2090 mg/L). Low pH values (2.5–2.8) and high dissolved concentrations of the same PTE were found in surface waters, up to 1500 m downstream from the mine. Nevertheless, concentrations of As, Ba and Pb in acid mine effluents and impacted surface waters are relatively low: 0.01–0.3 mg/L As, 0.002–0.03 mg/L Ba and 0.3–4.3 mg/L Pb. Analysis by X-ray diffraction and electron microscopy revealed the occurrence of lead–bearing barite and beudantite and the more common solid phases, reported elsewhere in similar environments including Fe-oxyhydroxides, jarosite, anglesite and plumbojarosite. Because the reported solubilities for barite and beudantite are very low under acidic conditions, these minerals may serve as the most important control in the mobility of As, Ba and Pb. In contrast, Fe-oxyhydroxides are relatively soluble under acidic conditions and, therefore, they may have a less significant role in PTE on-site immobilization.Mine-wastes and stream sediments show a light REE (LREE) and middle REE (MREE) enrichment relative to heavy REE (HREE). In contrast, acid mine effluents and surface waters are enriched in HREE relative to LREE. These results suggest that the LREE released during the oxidation of sulfides are captured by secondary (weathering) minerals, while the MREE are removed from the altered rocks. The low concentrations of LREE in acid stream water suggest that these elements can be retained in the sediments more strongly than HREE and MREE. One possible explanation for the sharp decrease in dissolved LREE might be their retention by low-solubility secondary minerals such as anglesite, barite and jarosite.

Historical mining has left complex problems in catchments throughout the world. Land managers are faced with making cost-effective plans to remediate mine influences. Remediation plans are facilitated by spatial mass-loading profiles that indicate the locations of metal mass-loading, seasonal changes, and the extent of biogeochemical processes. Field-scale experiments during both low- and high-flow conditions and time-series data over diel cycles illustrate how this can be accomplished. A low-flow experiment provided spatially detailed loading profiles to indicate where loading occurred. For example, SO 4 2 - was principally derived from sources upstream from the study reach, but three principal locations also were important for SO 4 2 - loading within the reach. During high-flow conditions, Lagrangian sampling provided data to interpret seasonal changes and indicated locations where snowmelt runoff flushed metals to the stream. Comparison of metal concentrations between the low- and high-flow experiments indicated substantial increases in metal loading at high flow, but little change in metal concentrations, showing that toxicity at the most downstream sampling site was not substantially greater during snowmelt runoff. During high-flow conditions, a detailed temporal sampling at fixed sites indicated that Zn concentration more than doubled during the diel cycle. Monitoring programs must account for diel variation to provide meaningful results. Mass-loading studies during different flow conditions and detailed time-series over diel cycles provide useful scientific support for stream management decisions.

Conceptual model for radionuclide release, Yucca Mountain, Nevada, USA by John C. Walton; Lubna Hamdan; Arturo Woocay (741-746).
A new conceptual model for release rate of radionuclides from the proposed repository for high level nuclear waste located at Yucca Mountain, Nevada is developed. The model predicts that heat generated from radioactive decay combined with the unsaturated environment will lead to an inward flow system that, under many relevant conditions, will slow the release of and sometimes sequester radionuclides at locations of higher heat release and lower water percolation. The amount of protection will be greatest for more concentrated waste forms such as spent fuel and less for glass waste forms. The redistribution and concentration of the radionuclides is anticipated to significantly delay radionuclide release and create a tendency towards gradual release over time that is independent of localized penetrations of metallic barriers.

In many forested headwater catchments, peak SO 4 2 - concentrations in stream water occur in the late summer or fall following drought potentially resulting in episodic stream acidification. The sources of highly elevated stream water SO 4 2 - concentrations were investigated in a first order stream at the Sleepers River watershed (Vermont, USA) after the particularly dry summer of 2001 using a combination of hydrological, chemical and isotopic approaches. Throughout the summer of 2001 SO 4 2 - concentrations in stream water doubled from ∼130 to 270 μeq/L while flows decreased. Simultaneously increasing Na+ and Ca2+ concentrations and δ34S values increasing from +7‰ towards those of bedrock S (∼+10.5‰) indicated that chemical weathering involving hydrolysis of silicates and oxidation of sulfide minerals in schists and phyllites was the cause for the initial increase in SO 4 2 - concentrations. During re-wetting of the watershed in late September and early October of 2001, increasing stream flows were accompanied by decreasing Na+ and Ca2+ concentrations, but SO 4 2 - concentrations continued to increase up to 568 μeq/L, indicating that a major source of SO 4 2 - in addition to bedrock weathering contributed to peak SO 4 2 - concentrations. The further increase in SO 4 2 - concentrations coincided with an abrupt decrease of δ34S values in stream water SO 4 2 - from maximum values near +10‰ to minimum values near −3‰. Soil investigations revealed that some C-horizons in the Spodsols of the watershed contained secondary sulfide minerals with δ34S values near −22‰. The shift to negative δ34S values of stream water SO 4 2 - indicates that secondary sulfides in C-horizons were oxidized to SO 4 2 - during the particularly dry summer of 2001. The newly formed SO 4 2 - was transported to the streams during re-wetting of the watershed contributing ∼60% of the SO 4 2 - during peak concentrations in the stream water. Thereafter, the contribution of SO 4 2 - from oxidation of secondary sulfides in C-horizons decreased rapidly and pedogenic SO 4 2 - reemerged as a dominant SO 4 2 - source in concert with decreasing SO 4 2 - concentrations in spring of 2002. The study provides evidence that a quantitative assessment of the sources of stream water SO 4 2 - in forested watersheds is possible by combining hydrological, chemical and isotopic techniques, provided that the isotopic compositions of all potential SO 4 2 - sources are distinctly different.

Knowledge of the natural background content of metals is important, but can be difficult to establish because the concentrations of substances dissolved in ground waters vary considerably with time and space. The main objective of the paper is to assess the natural background of five selected elements: As, Al, Cd, Pb and Hg. Each of these elements, with the exception of Al, is included in the Minimum list of pollutants and their indicators for which the EU Member States should establish threshold values (Daughter Groundwater Directive). The data of the Czech Hydrometeorological Institute which contains analyses obtained by regular monitoring of the quality of ground waters at intervals of 6 months has been used as the source information. This system incorporates ca. 450 monitoring sites which provide information about water in all the types of rocks penetrated by individual boreholes. Because of the low concentrations of certain elements (Hg, Pb and Cd in particular) a significant number of analytical results lie below the quantification limit of the analytical methods used. Therefore, conventional statistical methods for processing data were not applicable and alternative procedures were used. The Kaplan–Meier procedure was used within the NADA module for statistical analysis of data sets containing values below the quantification limit. The concentrations of monitored elements that can be considered natural background are suggested to be values of the third quartile, i.e. values that are less than or equal to 75% of analytical results in the assessed dataset. The remaining 25% of analytical results that exceed the proposed limit can be considered to be anomalies which may be natural or anthropogenic. Based on the statistical analysis of data specific values for the natural background content of elements in ground waters within particular types of lithology have been proposed. These can be considered the natural background values that apply within the whole of the territory of the Czech Republic.