Measurement and modeling of mercury complexation by dissolved organic matter isolates from freshwater and effluents of a major wastewater treatment plant

Dissolved organic matter (DOM) samples were obtained from a low-density urbanized area located upstream of Paris (along the Marne River, France) and from the treated effluents at the Paris main wastewater treatment plant. These samples were then fractionated according to their hydrophobicity. DOM fractions consisted of nanomolar to sub-micromolar fresh organic substances with extremely strong Hg-complexing ligands. The conditional stability constants (i.e. ; pH ∼ 6.8, I_NaCl = 0.5 M, T = 25 °C) of the Hg-DOM complexes formed were greater than 10²⁴ M⁻¹, for the reaction Hg²⁺ + L = HgL (with L as ligand). For upstream of Paris, thermodynamic calculations indicated that the vast majority of Hg-DOM was associated with hydrophobic DOM. In contrast, in the Paris main wastewater treatment plant effluents, Hg-DOM was mainly bound to hydrophilic DOM. Simple dilution calculations highlighted that due to the large DOM loading of urban discharges, the hydrophilic urban DOM ligands may commonly dominate Hg-DOM speciation in the downstream Seine River, except under extreme dilution (i.e. high water episodes or floods).     

Linking lithology and land use to sources of dissolved and particulate organic matter in headwaters of a temperate, passive-margin river system

A number of rivers have been found to transport highly aged organic matter [OM]; however, the sources of this aged material remain a matter of debate. One potential source may be erosion and weathering of headwater lithologies rich in ancient sedimentary OM. In this study, waters, suspended particulates, streambed sediments, rocks and soils from fourteen small headwater watersheds of a mid-size, temperate, passive margin river were sampled and characterized by Δ¹⁴C, δ¹³C, and POC/TPN ratios to identify sources of particulate and dissolved OM delivered to the river mainstem. These headwater sites encompass a range in lithology (OM-rich shales, OM-lean carbonate/mudstone facies, and OM-free crystalline rocks) and land use types (forested and agricultural), and allow investigation of the influence of agriculture and bedrock types on stream OM characteristics. Streams draining large areas of both agricultural land use and OM-rich lithology contain particulate OM [POM] that is more ¹⁴C-depleted than streams draining forested, shale-free watersheds. However, this is not sufficient to account for the significantly lower Δ¹⁴C-POC measured in the river mainstem. Dissolved OM [DOM] Δ¹⁴C are in all cases enriched compared to POM from the same stream, but are otherwise highly variable and unrelated to either land use or lithology. POC/TPN ratios were likewise highly variable. POC and DOC δ¹³C signatures were similar across all watersheds. Based on isotope mass balance, ¹⁴C-free fossil OM sources contribute 0-12% of total stream POM. Although these results do not unequivocally separate the influences of land use and lithology, watershed coverage by shale and agriculture are both important controls on stream Δ¹⁴C-POC. Thus export of aged, particle-associated OM may be a feature of river systems along both passive and active continental margins.     

Effects of sugar cane monocultures on origin and characteristics of dissolved organic matter in the Manguaba lagoon in northeast Brazil

Brazil has extensive sugar cane monocultures, which significantly alter hydrogeochemical material fluxes. We studied dissolved organic matter (OM) fluxes in the Manguaba lagoon-estuary system, which drains a sugar cane monoculture-dominated hinterland and discharges into the Atlantic coastal ocean. The OM fluxes into the lagoon originate from baseflow, field runoff and sugar cane factory effluents. In the study, dissolved organic carbon (DOC) concentration, δ¹³C DOC and UV absorbance were analysed along a freshwater-seawater salinity gradient that encompasses river (DOC 9-11 mg l⁻¹, δ¹³C −22.2‰ to −25.5‰); lagoon (4-11 mg l⁻¹, −20.5‰ to −24.8‰); estuary (3-9 mg l⁻¹, −22.6‰ to −25.3‰) and coastal waters (1.64 mg l⁻¹, −21‰) with different intra-seasonal runoff conditions. We used the carbon isotope data to quantify the sugar cane derived DOC. Where river water meets brackish lagoon water, substantial loss of DOC occurs during rainy conditions, when suspended sediment from eroded fields in the river is very high. During dry weather, at much lower suspension levels, DOC increases, however, presumably from addition of photolysed resuspended sedimentary OM. In the estuary, mixing of DOC is strictly conservative. Ca. 1/3 of riverine DOM discharged into the lagoon has a sugar cane source. Within the lagoon on avg. 20% of the bulk DOM is comprised of sugar cane DOM, whereas during heavy rainfall the amount increases to 31%, due to intensified drainage flow and soil erosion. In the estuary, 14-26% is of sugar cane origin. The sugar cane-derived component follows the mixing patterns of bulk DOM.     

我国南方岩溶区和北方黄土区的大气CO2效应

我国南方岩溶区与北方黄土区都是巨大的碳库。碳酸盐的溶蚀及再结晶是两个碳库与大气ＣＯ^２交换的重要过程。碳的区域平衡是评价化学风化消耗或逸散ＣＯ^２的基础。岩溶区与黄土区在地球化学风化的环境背景、溶蚀过程、产物运移和归宿等差异很大。黄土区化学风化消耗大气ＣＯ^２通量较岩溶区小。目前评价两类地区土壤与大气ＣＯ^２的源汇关系尚不成熟,需要定量认识土壤ＣＯ^２与下伏碳酸盐岩溶蚀或与下伏黄土次生碳酸盐化作用。岩溶区湖泊沉积物中有机质分解产生的ＨＣＯ^３－制约外源及内生碳酸盐溶解和自生碳酸盐形成。     

Sr fluxes and Sr/Sr characterization of river waters from a karstic versus granitic watershed in the Yangtze River

The watershed in the southern Jiangxi Province (Jiangxi Province is called simply Gan) (SGW) and the watershed in the central Guizhou Province (Guizhou Province is called simply Qian) (CQW) are two subtropical watersheds of the Yangtze River in China. Both watersheds have similar latitudes and climate, but distinct differences in basin lithology. These similarities and differences provide a good natural laboratory in which to investigate weathering processes and Sr end-members in river waters. This work aims to identify and contrast the sources, fluxes and controls on Sr isotopic composition in the river waters of these two areas. Results showed that the ⁸⁷Sr/⁸⁶Sr in the SGW waters ranged from 0.716501 to 0.724931, with dissolved Sr averaging 27 μg l^− 1. Rhyolites and granites are two major sources for the dissolved Sr. The SGW waters receive 42% of their Sr from silicates weathering, 32% from carbonates and 3.2% from evaporites. ⁸⁷Sr/⁸⁶Sr in the CQW waters has a lesser variation from 0.707694 to 0.710039, but higher Sr contents (average of 208 μg l^− 1). Dolomite, limestone and dolomitic limestone are major sources of Sr in the waters. The CQW waters receive 69% of their Sr from carbonates, 1.7% from silicates and 0.9% from evaporites. The chemical erosion rate and Sr flux in the CQW are 122 t km^− 2 a^− 1 and 0.079 t km^− 2 a^− 1, respectively, which are higher than those of the SGW (56 t km^− 2 a^− 1 and 0.021 t km^− 2 a^− 1, respectively). These data suggest that the intensive carbonates weathering occurred in the karstic area in the upper-reach of the Yangtze River exert great influence on the high Sr concentration and low Sr isotopic ratios in the River.     

The role of trace minerals in chemical weathering in a high-elevation granitic watershed (Estibère, France): chemical and mineralogical evidence

We investigated chemical weathering in a high elevation granitic environment in three selected watersheds located in the Pyrenees (France). The sites were located on glacial deposits derived from similar Hercynian (∼300 Ma) granites characterized by the occurrence of zoned plagioclases and trace calcic phases (epidote, prehnite, sphene, apatite). The surface waters at those sites show high Ca/Na molar ratios (>1) which could not be explained by the dissolution of the major plagioclase (oligoclase) present in the rocks. The coupled approach of investigating stream water chemistry and the mineralogy and chemistry of rocks and soils allowed us to explore the role of the weathering of trace calcic minerals in calcium export at the watershed scale. The weathering of the trace calcic minerals which represent ∼ 1% of the total rock volume are responsible for more than 90% of the calcium export at the sites. Annual cationic fluxes (∼ 23.10⁴ eq/km²/yr) calculated for the Estibère watershed are among the highest reported for high elevation systems draining granitic rocks and ∼ 80% of this annual cationic flux can be attributed to the weathering of trace calcic phases. Calculations based on isotopic values (⁸⁷Sr/⁸⁶Sr) go in the same direction. Except apatite, the trace calcic phases appear to be mainly silicates, thus the type of chemical weathering observed in the Estibère watershed may have an influence on atmospheric CO₂ consumption by granite weathering. However, comparison with other watersheds draining granitic environments worldwide, and with the two other sites in the Pyrenees, indicate that the role of trace calcic phases is important in most young environments exposed to chemical weathering (e.g., high elevation catchments on glacial deposits). Other factors such as the date of glacial retreat, the physical denudation rate, the hydrological functioning of the watershed and the nature and structure of the soil cover are also important.     

Present weathering rates in a humid tropical watershed: Nsimi, South Cameroon

The study of biogeochemical and hydrological cycles in small experimental watersheds on silicate rocks, common for the Temperate Zone, has not yet been widely applied to the tropics, especially humid areas. This paper presents an updated database for a six-year period for the small experimental watershed of the Mengong brook in the humid tropics (Nsimi, South Cameroon). This watershed is developed on Precambrian granitoids (North Congo shield) and consists of two convexo-concave lateritic hills surrounding a large flat swamp covered by hydromorphic soils rich in upward organic matter. Mineralogical and geochemical investigations were carried out in the protolith, the saprolite, the hillside lateritic soils, and the swamp hydromorphic soils. Biomass chemical analyses were done for the representative species of the swamp vegetation. The groundwater was analysed from the parent rock/saprolite weathering front to the upper fringe in the hillside and swamp system. The chemistry of the wet atmospheric and throughfall deposits and the Mengong waters was monitored.In the Nsimi watershed the carbon transfer occurs primarily in an organic form and essentially as colloids produced by the slow biodegradation of the swamp organic matter. These organic colloids contribute significantly to the mobilization and transfer of Fe, Al, Zr, Ti, and Th in the uppermost first meter of the swamp regolith. When the organic colloid content is low (i.e., in the hillside groundwater), Th and Zr concentrations are extremely low (<3 pmol/L, ICP-MS detection limits). Strongly insoluble secondary thorianite (ThO₂) and primary zircon (ZrSiO₄) crystals control their mobilization, respectively. This finding thus justifies the potential use of both these elements as inert elements for isoelement mass balance calculations pertaining to the hillside regolith.Chloride can not be used as a conservative tracer of hydrological processes and chemical weathering in this watershed. Biogenic recycling significantly influences the low-Cl input fluxes. Sodium is a good tracer of chemical weathering in the watershed. The sodium solute flux corrected from cyclic salt input was used to assess the chemical weathering rate. Even though low (2.8 mm/kyr), the chemical weathering rate predominates over the mechanical weathering rate (1.9 mm/kyr). Compared to the Rio Icacos watershed, the most studied tropical site, the chemical weathering fluxes of silica and sodium in the Mengong are 16 and 40 times lower, respectively. This is not only related to the protective role of the regolith, thick in both cases, but also to differences in the hydrological functioning. This is to be taken into account in the calculations of the carbon cycle balance for large surfaces like that of the tropical forest ecosystems on a stable shield at the global level.     

Properties of fluorescent dissolved organic matter in the Gironde Estuary

The isolation, characterization and study of the properties of aquatic dissolved organic matter (DOM) still represent a challenge because of the heterogeneity, complexity and low concentration of organic material in natural waters. Based on its ability to interact with contaminants and thus to modify their transport and bioavailability, DOM is of interest for environmental purposes. The objective of this work was to better characterize DOM in the Gironde Estuary (southwestern France). The estuary represents an exchange zone between the continent and the Atlantic Ocean and conditions the transfer of organic and inorganic substances from the continental to the oceanic environment. Several samples were collected along the estuary during three cruises in 2002 and 2006. They were analysed using excitation–emission matrix (EEM) spectroscopy, a sensitive technique that allows direct analysis of water samples. Fluorescent DOM and dissolved organic carbon (DOC) did not behave conservatively in this estuarine system, i.e. the organic material did not undergo simple dilution from the upstream to the downstream part of the estuary. A seasonal variability in DOC content was pointed out, whereas few seasonal variations in DOM fluorescence were observed. DOM sources and processing in the estuary were further evaluated by determining two fluorescence indices – the humification index (HIX) and the index of recent autochthonous contribution (BIX). By applying these indices, the relative degree of humification (HIX) and autotrophic productivity (BIX) could be assessed. Based on the fluorescence and DOC results, the estuary was divided into three zones depending on salinity (S) and characterized by specific DOM: (i) A turbid zone of low salinity (S < 5) and high suspended particulate matter concentration with increase in the intensities of the α′ and α fluorophores, characteristic of humic-like compounds. (ii) A mid-estuarine zone (5 < S < 25) characterized by low autotrophic productivity and containing strongly degraded organic material, as shown by the low values of BIX and high values of HIX. (iii) A higher salinity area (S > 25) characterized by increased autotrophic productivity and a marked marine influence, and associated with high and low values of BIX and HIX, respectively. The HIX and BIX indices were shown as useful tools for readily defining and classifying DOM characteristics in estuarine waters.     

典型岩溶水系统碳汇通量估算

现代岩溶学研究成果表明,碳酸盐岩在全球碳循环中响应极其迅速,水循环过程中的碳汇效应显著。本研究选取广西桂林寨底地下河系统、广西环江大安地下河系统、重庆北碚青木关地下河系统三个典型岩溶地下水系统,利用各系统地下河的流量和HCO3-浓度的监测资料,采用简单化学平衡模式法估算碳汇通量(CO2)。结果显示,寨底地下河系统的单位面积年碳汇通量为68.82 t/(km2.a),大安地下河系统的单位面积年碳汇通量为81.18 t/(km2.a),青木关地下河系统的单位面积年碳汇通量为100.07 t/(km2.a)。分析认为同一个岩溶水系统的结构特征和环境条件基本上是稳定的;地下河的流量和HCO3-浓度是影响岩溶碳汇强度的关键因素,尤其是地下河流量的变化对碳汇强度的影响显著;不同岩溶水系统的碳汇通量不但受水化学条件和地下水动力条件的控制,同时受土地利用变化的影响。该研究对于改进碳循环模型和评价岩溶地质碳汇有重要意义。     

Ca/Sr and Sr isotope systematics of a Himalayan glacial chronosequence: carbonate versus silicate weathering rates as a function of landscape surface age

We explored changes in the relative importance of carbonate vs. silicate weathering as a function of landscape surface age by examining the Ca/Sr and Sr isotope systematics of a glacial soil chronosequence located in the Raikhot watershed within the Himalaya of northern Pakistan. Bedrock in the Raikhot watershed primarily consists of silicate rock (Ca/Sr ≈ 0.20 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.77 to 1.2) with minor amounts of disseminated calcite (Ca/Sr ≈ 0.98 to 5.3 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.79 to 0.93) and metasedimentary carbonate (Ca/Sr ≈ 1.0 to 2.8 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.72 to 0.82). Analysis of the exchangeable, carbonate, and silicate fractions of seven soil profiles ranging in age from ∼0.5 to ∼55 kyr revealed that carbonate dissolution provides more than ∼90% of the weathering-derived Ca and Sr for at least 55 kyr after the exposure of rock surfaces, even though carbonate represents only ∼1.0 wt% of fresh glacial till. The accumulation of carbonate-bearing dust deposited on the surfaces of older landforms partly sustains the longevity of the carbonate weathering flux. As the average landscape surface age in the Raikhot watershed increases, the Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios released by carbonate weathering decrease from ∼3.6 to ∼0.20 μmol/nmol and ∼0.84 to ∼0.72, respectively. The transition from high to low Ca/Sr ratios during weathering appears to reflect the greater solubility of high Ca/Sr ratio carbonate relative to low Ca/Sr ratio carbonate. These findings suggest that carbonate weathering controls the dissolved flux of Sr emanating from stable Himalayan landforms comprising mixed silicate and carbonate rock for tens of thousands of years after the mechanical exposure of rock surfaces to the weathering environment.     

Global significance of the carbon cycle in the karst dynamic system: evidence from geological and ecological processes

On the basis of proposing the existence of a karst carbon cycle and carbon sink at a watershed scale, this paper provides four pieces of evidence for the integration of geology and ecology during the carbon cycle processes in the karst dynamic system, and estimated the karst carbon sink effect using the methods of comparative monitoring of paired watersheds and the carbon stable isotope tracer technique. The results of the soil carbon cycle in Maocun, Guilin, showed that the soil carbon cycle in the karst area, the weathering and dissolution of carbonate rocks under the soil, resulted in a lower soil respiration of 25% in the karst area than in a non-karst area (sandstone and shale), and the carbon isotope results indicated that 13.46% of the heavy carbon of the limestone is involved in the soil carbon cycle. The comparative monitoring results in paired watersheds, suggesting that the HCO₃^- concentration in a karst spring is 10 times that of a rivulet in a non-karst area, while the concentration of inorganic carbon flux is 23.8 times. With both chemical stoichiometry and carbon stable isotopes, the proportion of carbon in karst springs derived from carbonate rocks was found to be 58.52% and 37.65% respectively. The comparison on carbon exchange and isotopes at the water-gas interface between the granite and carbonate rock basins in the Li River showed that the CO₂ emission of the karst water is 10.92 times that of the allogenic water from the non-karst area, while the carbon isotope of HCO₃^- in karst water is lighter by 8.62‰. However, this does not mean that the karst water body has a larger carbon source effect. On the contrary, it means the karst water body has a greater karst carbon sink effect. When the karst subterranean stream in Zhaidi, Guilin, is exposed at the surface, carbon-rich karst water stimulated the growth of aquatic plants. The values of carbon stable isotopes in the same species of submerged plants gradually becomes heavier and heavier, and the 512 m flow process has a maximum range of 15.46‰. The calculation results showed that 12.52% of inorganic carbon is converted into organic carbon. According to the data that has been published, the global karst carbon sink flux was estimated to be 0.53-0.58 PgC/a, equivalent to 31.18%-34.41% of the global forest carbon sink flux. In the meanwhile, the karst carbon sink flux in China was calculated to be 0.051 PgC/a, accounting for 68% of its forest carbon sink flux.     

Sr isotopes as a tracer of weathering processes and dust inputs in a tropical granitoid watershed, Luquillo Mountains, Puerto Rico

Sr isotope data from soils, water, and atmospheric inputs in a small tropical granitoid watershed in the Luquillo Mountains of Puerto Rico constrain soil mineral development, weathering fluxes, and atmospheric deposition. This study provides new information on pedogenic processes and geochemical fluxes that is not apparent in watershed mass balances based on major elements alone. ⁸⁷Sr/⁸⁶Sr data reveal that Saharan mineral aerosol dust contributes significantly to atmospheric inputs. Watershed-scale Sr isotope mass balance calculations indicate that the dust deposition flux for the watershed is 2100 ± 700 mg cm⁻² ka⁻¹. Nd isotope analyses of soil and saprolite samples provide independent evidence for the presence of Saharan dust in the regolith. Watershed-scale Sr isotope mass balance calculations are used to calculate the overall short-term chemical denudation velocity for the watershed, which agrees well with previous denudation rate estimates based on major element chemistry and cosmogenic nuclides. The dissolved streamwater Sr flux is dominated by weathering of plagioclase and hornblende and partial weathering of biotite in the saprock zone. A steep gradient in regolith porewater ⁸⁷Sr/⁸⁶Sr ratio with depth, from 0.70635 to as high as 0.71395, reflects the transition from primary mineral-derived Sr to a combination of residual biotite-derived Sr and atmospherically-derived Sr near the surface, and allows multiple origins of kaolinite to be identified.     

A novel index of susceptibility of rivers and their catchments to acidification in regions subject to a maritime influence

A simple, unifying approach to classifying quantitatively the susceptibility of catchment soils and surface waters to acidification is suggested. In areas subject to a strong maritime influence, such as the UK and substantial parts of NW Europe, wherever soil mineral weathering rates are low and soils are unfertilised, atmospherically derived base cations of maritime origins have a greater effect than those derived from biogeochemical weathering on the exchangeable soil base cations. This is directly reflected in the relative base cation concentrations of the associated drainage waters, which become increasingly Na-dominated. Using 10 sub-catchments of the River Dee in north-eastern Scotland, it is shown here that the extent of Na dominance, the ratio of Na⁺ to ΣNa⁺+Ca²⁺+Mg²⁺, at any point in a river provides a quantitative index of the upstream weathering rate and thus of the susceptibility of the river concerned to acidification under diverse flow conditions. Data from a further 58 sub-catchments from the same river system, and from 4 other catchments from around Scotland, were used to validate this theory.     

Silicate and carbonate mineral weathering in soil profiles developed on Pleistocene glacial drift (Michigan, USA): Mass balances based on soil water geochemistry

Geochemistry of soil, soil water, and soil gas was characterized in representative soil profiles of three Michigan watersheds. Because of differences in source regions, parent materials in the Upper Peninsula of Michigan (the Tahquamenon watershed) contain only silicates, while those in the Lower Peninsula (the Cheboygan and the Huron watersheds) have significant mixtures of silicate and carbonate minerals. These differences in soil mineralogy and climate conditions permit us to examine controls on carbonate and silicate mineral weathering rates and to better define the importance of silicate versus carbonate dissolution in the early stage of soil-water cation acquisition.Soil waters of the Tahquamenon watershed are the most dilute; solutes reflect amphibole and plagioclase dissolution along with significant contributions from atmospheric precipitation sources. Soil waters in the Cheboygan and the Huron watersheds begin their evolution as relatively dilute solutions dominated by silicate weathering in shallow carbonate-free soil horizons. Here, silicate dissolution is rapid and reaction rates dominantly are controlled by mineral abundances. In the deeper soil horizons, silicate dissolution slows down and soil-water chemistry is dominated by calcite and dolomite weathering, where solutions reach equilibrium with carbonate minerals within the soil profile. Thus, carbonate weathering intensities are dominantly controlled by annual precipitation, temperature and soil pCO₂. Results of a conceptual model support these field observations, implying that dolomite and calcite are dissolving at a similar rate, and further dissolution of more soluble dolomite after calcite equilibrium produces higher dissolved inorganic carbon concentrations and a Mg²⁺/Ca²⁺ ratio of 0.4.Mass balance calculations show that overall, silicate minerals and atmospheric inputs generally contribute <10% of Ca²⁺ and Mg²⁺ in natural waters. Dolomite dissolution appears to be a major process, rivaling calcite dissolution as a control on divalent cation and inorganic carbon contents of soil waters. Furthermore, the fraction of Mg²⁺ derived from silicate mineral weathering is much smaller than most of the values previously estimated from riverine chemistry.     

Geochemical factors controlling free Cu ion concentrations in river water

Copper speciation was determined monthly at seven sites on four rivers in southern New England to understand which geochemical factors control free metal ion concentrations in river water. Samples were conventionally filtered (<0.45 μm) and then ultrafiltered (3.000 molecular weight cut-off) to determine Cu speciation in the truly dissolved size fraction. Differential pulse anodic stripping voltammetry (DPASV) was used to quantify natural organic complexation and cathodic stripping square wave voltammetry (CSSWV) to measure directly both Cu sulfide complexes and total EDTA concentrations. The results showed both dissolved organic matter (DOM) and sulfide complexation dominate Cu speciation and control the concentrations of free ion. Free Cu²⁺ was calculated to be in the subnanomolar range for the majority of the year. Only in the winter months, when concentrations of DOM and metal sulfides complexes were at a minimum were free metal ions directly measurable by DPASV at low nanomolar concentrations. The extent of sulfide complexation appears to be dominated by the size of headwater marshes (upstream sampling sites) and by the amount of sewage treatment plant effluent (downstream sites). DOM complexation was related to the organic matter composition and followed model organic ligands. Indirect evidence suggests variations in river water pH and Ca²⁺ (metal competition) has only a minor role in Cu complexation. Measured concentrations of total EDTA suggest this synthetic ligand can control Cu speciation in some highly developed watersheds; however, competition from Ni (and possibly Fe) limits the extent of this complexation.     

Rates of Biotite Weathering,and Clay Mineral Transformation and Neoformation,Determined from Watershed Geochemical Mass-Balance Methods for the Coweeta Hydrologic Laboratory,Southern Blue Ridge Mountains,North Carolina,USA

Biotite is a common constituent of silicate bedrock. Its weathering releases plant nutrients and consumes atmospheric CO₂. Because of its stoichiometric relationship with its transformational weathering product and sensitivity to botanical activity, calculating biotite weathering rates using watershed mass-balance methods has proven challenging. At Coweeta Hydrologic Laboratory the coupling of biotite to its transformational weathering product is only valid if the stoichiometric relationship for the two phases is known; this relationship is unlikely layer-for-layer. Rates of biotite weathering and transformation of its secondary weathering product at the Coweeta Hydrological Laboratory are comparable with other Appalachian watersheds. The magnitude and sign of the difference between field- and laboratory-determined biotite weathering rates are similar to those of other silicate minerals. The influence of major-cation proportions in biomass on the rates of biotite weathering and transformational weathering product is greatest for watersheds with high biomass aggradation rates. The watershed with the lowest bedrock reactivity and highest flushing rate yielded the highest gibbsite formation rate of ~500 mol ha^?1 year^?1 and lowest kaolin-group mineral formation rates of 4–78 mol ha^?1 year^?1. The kaolin-group mineral formation rate increases as bedrock reactivity increases and flushing rate decreases to a maximum of ~300 mol ha^?1 year^?1, with a similar minimum gibbsite formation rate. The relative differences in bedrock reactivity and flux of water through Coweeta Hydrological Laboratory watersheds studied appear to be invariant over geologic timescales.     

Magnitudes, spatial scales and processes of environmental antimony mobility from orogenic gold–antimony mineral deposits, Australasia

Antimony (Sb) is strongly concentrated into hydrothermal mineral deposits, commonly with gold, in metasedimentary sequences around the Pacific Rim. These deposits represent potential point sources for Sb in the downstream environment, particularly when mines are developed. This study documents the magnitude and scale of Sb mobility near some mineral deposits in Australia and New Zealand. Two examples of New Zealand historic mining areas demonstrate that natural groundwater dissolution of Sb from mineral deposits dominates the Sb load in drainage waters, with Sb concentrations between 3 and 24 μg/L in major streams. Mine-related discharges can exceed 200 μg/L Sb, but volumes are small. Sb flux in principal stream waters is ca 1–14 mg/s, compared to mine tunnel fluxes of ca 0.001 mg/s. Dissolved Sb is strongly attenuated near some mine tunnels by adsorption on to iron oxyhydroxide precipitates. Similar Sb mobilisation and attenuation processes are occurring downstream of the historic/active Hillgrove antimony–gold mine of New South Wales, Australia, but historic discharges of Sb-bearing debris has resulted in elevated Sb levels in stream sediments (ca 10–100⁺ mg/kg) and riparian plants (up to 100 mg/kg) for ca 300 km downstream. Dissolution of Sb from these sediments ensures that river waters have elevated Sb (ca 10–1,000 μg/L) over that distance. Total Sb flux reaching the Pacific Ocean from the Hillgrove area is ca 8 tonnes/year, of which 7 tonnes/year is particulate and 1 tonne/year is dissolved.     

Seasonality of bedrock weathering chemistry and CO2 consumption in a small watershed, the White River, Vermont

The draw down of CO₂ from the atmosphere during mineral weathering plays a major role in the global budget of this greenhouse gas. Silicate minerals remove twice the CO₂ of carbonate minerals per mole of calcium in runoff during weathering. Bedrock weathering chemistry was investigated in the White River watershed of northeastern USA to investigate whether there are seasonal differences in carbonate and silicate weathering chemistry. Geographic Information Systems analyses of bedrock geology were combined with major element concentrations in river waters to gain an understanding of the consistency of mineral weathering during three seasons. The percent of carbonate mineralogy comprising the bedrock in tributaries of the White River varied from less than 5% to 45% by area. A mass balance calculation using major element concentrations in waters was applied to estimate the seasonal relationships between bedrock geology and bicarbonate flux. In all tributaries and the main stem of the White River the highest calculated percent of bicarbonate from carbonate mineral weathering was measured in the late fall. The results suggest that carbonate and silicate bedrock weathering processes are seasonally controlled. Thus single season sampling could not accurately represent an entire year's geochemical budget. In the White River, water samples obtained solely during the summer would consistently underestimate the total yearly source of bicarbonate from carbonate bedrock weathering. The same sample set would also provide data that would lead to an underestimation of the yearly atmospheric CO₂ draw down by bedrock weathering in the watershed. For example at four of the seven locations studied there was an almost two-fold difference between summer and spring calculated atmospheric CO₂ consumption rates.     

Fractionation of dissolved organic matter affected by polyvalent metal cations

The purpose of the study was to evaluate the influence of polyvalent cations known to form complexes with natural organic substances on the operational fractionation of dissolved organic matter (DOM) using XAD-8 adsorber resin. Dissolved organic matter solutions from a forest floor were treated with increasing concentrations of polyvalent metal cations (Ca²⁺, Al³⁺, Fe³⁺) at different pH levels. Then the concentrations of total dissolved organic carbon (DOC) and the distribution between hydrophilic and hydrophobic DOC were determined. The concentrations of total DOC decreased slightly when the C/metal ratio was less than 10, especially for Al and Fe. Hydrophilic DOC increased and hydrophobic DOC decreased with increasing concentrations of metal cations. Effects increased in the order Ca<Al<Fe and were more pronounced at low DOC concentrations and high pH values. The reason for the reduction of the DOC concentrations seemed to be the formation of insoluble metal–DOM complexes, while soluble metal–DOM complexes may induce an alteration of the distribution between hydrophilic and hydrophobic DOC. Thus, the polyvalent cations and their concentration need to be considered when DOM fraction distributions, determined with XAD-8 resin, of different waters are compared, especially at low DOC contents and high pH.