Principal biogeochemical factors affecting the speciation and transport of mercury through the terrestrial environment

It is increasingly becoming known that mercury transport and speciation in the terrestrial environment play major roles in methyl-mercury bioaccumulation potential in surface water. This review discusses the principal biogeochemical reactions affecting the transport and speciation of mercury in the terrestrial watershed. The issues presented are mercury-ligand formation, mercury adsorption/desorption, and elemental mercury reduction and volatilization. In terrestrial environments, OH-, Cl- and S- ions have the largest influence on ligand formation. Under oxidized surface soil conditions Hg(OH)2, HgCl2, HgOH+, HgS, and Hg0 are the predominant inorganic mercury forms. In reduced environments, common mercury forms are HgSH+, HgOHSH, and HgClSH. Many of these mercury forms are further bound to organic and inorganic ligands. Mercury adsorption to mineral and organic surfaces is mainly dictated by two factors: pH and dissolved ions. An increase in Cl- concentration and a decrease in pH can, together or separately, decrease mercury adsorption. Clay and organic soils have the highest capability of adsorbing mercury. Important parameters that increase abiotic inorganic mercury reduction are availability of electron donors, low redox potential, and sunlight intensity. Primary factors that increase volatilization are soil permeability and temperature. A decrease in mercury adsorption and an increase in soil moisture will also increase volatilization. The effect of climate on biogeochemical reactions in the terrestrial watershed indicates mercury speciation and transport to receiving water will vary on a regional basis.     

The chemistry of aluminum in the environment

There is increased concern over the effects of elevated concentrations of Al in the environment. Unfortunately, studies of the environmental chemistry and toxicity of Al have been limited by our understanding of the processes regulating the aqueous concentration, speciation and bioavailability of this element.Although Al is the most abundant metallic element in the Earth's crust, it is highly insoluble and generally unavailable to participate in biogeochemical reactions. However, under highly acidic or alkaline conditions, or in the presence of complexing ligands, elevated concentrations may be mobilized to the aquatic environment. Ecologically significant concentrations of Al have been reported in surface waters draining acid-sensitive regions that are receiving elevated inputs of acidic deposition. Acid- sensitive watersheds are characterized by limited release of basic cations (Ca²⁺, Mg²⁺, Na⁺, K⁺) and/or retention of strong acid anions (SO₄ ^2–, NO₃ ^–, Cl^–). Under these conditions inputs of strong acids are not completely neutralized, but rather acidic water is exported from the terrestrial environment. It has been hypothesized that acidic deposition to acid-sensitive watersheds mobilizes Al within the mineral soil, causing elevated concentrations in soil solutions and surface waters. As a result of mineral phase solubility constraints, concentrations of aqueous Al increase exponentially with decreases in pH below 6.0.Monomeric Al occurs as a series of complexes in the aqueous environment, including aquo, OH^–, F^–, SO₄ ^2–, HCO₃ ^– and organic species. Of these aquo, OH^–, F^– and organic complexes are the most significant in natural waters.Elevated concentrations of Al are ecologically significant because: 1) Al is an important pH buffer in acidic waters, regulating the lower limit of pH values following acidification by strong acids; 2) through adsorption and coagulation reactions, Al may alter the cycling and availability of important elements like phosphorus, organic carbon and certain trace metals; 3) Al may serve as a coagulant facilitating the removal of light attenuating materials, thereby increasing the clarity and decreasing the thermal stability of lakes; and 4) Al is potentially toxic to organisms. Better understanding of the chemistry and speciation of Al is essential to assess these effects.     

Movement and transformation of35S-labelled sulphate in the soil of a heavily polluted site in the Northern Czech Republic

Changes in chemistry and vertical distribution of³⁵S were investigated in column experiments using intact topsoil and repacked mineral soil horizons 1 to 20 weeks after tracer application (901 kBq³⁵S-SO₄ ^2– per column 6.5 cm in diameter). Horizons O, A, AE and Bvs of an Orthic Podzol were incubated at 20°C and wetted twice a week with 11 mm of natural throughfall precipitation (38.5 mg S0₄ ^2– L^–1-, pH 3.3). The top 35 cm of the soil contained 1,290 kg S ha^–1, or 18 times more than is the annual atmospheric S input (71.4 kg S ha^–1 yr^–1). Of this amount, 17.8 % was stored as inorganic sulphate S, 4.6 % as reduced inorganic S, and 77.6 % as organic S. In O + A and AE, free sulphate was the most abundant³⁵S form, while in Bvs the 35S activity of free and adsorbed sulphate was similar. The proportion of adsorbed sulphate increased with depth, averaging 23, 30 and 47 % of total inorganic sulphate³⁵S in O + A, AE and Bvs, respectively. Total specific activity of chemically transformed³⁵S (i.e., of reduced inorganic S and organic S) constituted 3.4, 3.8 and 105 % of inorganic sulphate³⁵S activity in O + A, AE and Bvs, respectively, in averaged weeks 2–4, and 7.5, 6.4 and 39.6 % in averaged weeks 11–13 in O+A, AE and Bvs, respectively. The turnover time of C-bonded³⁵S was shorter than that of ester sulphate³⁵S. An increase in FeS_2– ³⁵S with time indicated anaerobic conditions suitable for bacterial sulphate reduction. After 13 weeks, 68 % of the tracer was found deeper than 8 cm below soil surface.     

The hydrolytic products of aluminum and their biological significance

The relative distribution of Al between its various organic and inorganic complexes dictates its mobility in the environment, bioavailability, and toxicity. In recent years, there has been significant progress made in understanding the differential bioavailability and toxicity of various chemical species of Al to plants and certain aquatic organisms. Far less information concerning chemical speciation and differential uptake and transport of Al in humans is available. Among the important inorganic complexes of interest are the hydrolyzed-Al species, particularly the nonequilibrium, metastable polynuclear complexes, which form readily, have a fairly wide stability range, and have been demonstrated toxic to plants and fish. In recent years²⁷Al NMR spectroscopy has provided significant direct information on the polynuclear complexes existing in a wide range of aqueous solutions. The [Al₁₂O₄(OH)_24+n(H₂O)_12–n]^(7–n)+ polynuclear complex is often found to be the predominant species in partially neutralized Al solutions and has recently been demonstrated to be more toxic to certain plants than the hexaaqua Al cation. It is also the principal component of Al-chlorohydrate, a highly soluble antiperspirant, present in many hydrolyzed Al solutions utilized in water and waste water treatment, and, as hypothesized herein, a primary constituent of many hydroxide gels utilized as antacids. This polynuclear has a wide pH stability range, reportedly forms copolynuclears with Si, and contains tetrahedrally coordinated Al within its structure, all features that may be relevant to the recently reported properties of Al associated with neuritic plaque cores.     

Influences of Suspended Particles on the Runoff of Pesticides from an Agricultural Field at Askim, SE-Norway

Field and laboratory experiments were conducted to study the loss of particles from agricultural fields, and the role of suspended particles in carrying pesticides in surface runoff and drainage water. Propiconazole, a widely used fungicide was applied to experimental fields located at Askim, SE-Norway. Samples from surface runoff and drainage water were collected and analyzed for sediment mass, pesticides, particulate and dissolved organic carbon through a whole year. The surface soil and the runoff material were characterized by its particle size distribution, organic carbon content in size fractions and its ability to bind propiconazole. The results show that (1) particle runoff mostly occurred during the rainfall event shortly after harrowing in autumn. The highest particle concentration observed in the surface runoff water was 4600 mg l^–1, and in the drainage water 1130 mg l^–1; (2) the erosion of surface soil is size selective. The runoff sediment contained finer particle/aggregates rich in organic matter compared to its original surface soil; (3) the distribution coefficient (K _d) of propiconazole was significantly higher in the runoff sediment than in the parent soil. According to our calculation, particle-bound propiconazole can represent up to 23% of the total amount of propiconazole in a water sample with a sediment concentration of 7600 mg l^–1, which will significantly influence the transport behavior of the pesticide.     

Nitrate reductase and urease enzyme activity in the marine diatom<Emphasis Type="Italic"> Thalassiosira weissflogii</Emphasis> (Bacillariophyceae): interactions among nitrogen substrates

The dissolved nitrogen pool in aquatic systems is comprised of many different nitrogen forms, both inorganic and organic. Interaction among these nitrogen forms at the level of uptake and enzyme activity is, with the exception of NH₄⁺ and NO₃^–, not completely understood. Nitrate reductase (NR) and urease (UA) activities in the marine diatom Thalassiosira weissflogii (Grunow) Fryxell et Hasle were measured in NO₃^–, NH₄⁺, and urea-sufficient cultures before and after challenge additions of NH₄⁺, NO₃^–, and urea in a factorial design. NR and UA were constitutively expressed during growth on NO₃^–, NH₄⁺, and urea. Growth on NH₄⁺ or urea resulted in NR activities that were <10% of the activity observed in the NO₃^–-grown culture, while growth on NO₃^– resulted in UA values that were ~35% of the activities during growth on either NH₄⁺ or urea. The addition of NH₄⁺ or urea to NO₃^–-grown cultures resulted in an immediate decrease in cellular NO₃^– uptake rate, which was not mirrored by an immediate repression of in vitro NR activity; however, the diel peak in NR was suppressed in these challenge experiments. The addition of NO₃^– or NH₄⁺ to urea-grown cultures resulted in non-significant decreases in the urea uptake rate. UA was not impacted by NO₃^– addition, but NH₄⁺ addition significantly decreased UA throughout the experiment. These studies demonstrate that the uptake and assimilation of NO₃^– and urea may not be subject to the same internal feedback mechanism when challenged with other nitrogen substrates.Communicated by J.P. Grassle, New Brunswick     

Influence of human-induced disturbance on benthic microbial metabolism in the Pichavaram mangroves,Vellar–Coleroon estuarine complex,India

Large areas of mangroves in India are heavily disturbed by cattle grazing, hypersalinity, and other human-induced impacts. In two disturbed Avicennia marina forests and two undisturbed A. marina and Rhizophora apiculata forests in the Pichavaram mangroves of the Vellar–Coleroon estuarine complex, southeast India, we measured the rates and pathways of microbial decomposition of soil organic matter to determine if human impact is altering biogeochemical activity within these stands. Rates of total carbon oxidation (T_COX) were higher in the undisturbed A. marina forest (mean 199 mol C m^–2 year^–1) than in the two impacted stands (43 and 79 mol C m^–2 year^–1); rates of total carbon oxidation in the R. apiculata forest averaged 75 mol C m^–2 year^–1. Sulphate reduction (range 21–319 mmol S m^–2 day^–1) was the major decomposition pathway (65–85% of T_COX), except at the most disturbed forest (30% of T_COX). Rates of sulphate reduction at all sites peaked in sub-surface soils to a depth of about 1 m, leading to little carbon burial (3–5% of total C input). There was some evidence of measurable iron and manganese reduction in association with tree roots. Rates of microbial activity were rapid in comparison with rates measured in other mangrove soils, reflecting high rates of phytoplankton production and organic matter retention in this lagoon. Human-induced disturbance creates a sharp zonation of dry, hypersaline soil overlying less saline, wetter soil, suppressing surface microbial and root growth. We conclude that this vertical alteration of soil characteristics and biogeochemistry shifts the cycling of nutrients between trees and microbes to a disequilibrium state, partly explaining why mangroves are stunted in these declining forests.Communicated by G. F. Humphrey, Sydney     

Nitrogen Export from an Agriculture Watershed in the Taihu Lake Area, China

Temporal changes in nitrogen concentrations and stream discharge, as well as sediment and nitrogen losses from erosion plots with different land uses, were studied in an agricultural watershed in the Taihu Lake area in eastern China. The highest overland runoff loads and nitrogen losses were measured under the upland at a convergent footslope. Much higher runoff, sediment and nitrogen losses were observed under upland cropping and vegetable fields than that under chestnut orchard and bamboo forest. Sediment associated nitrogen losses accounted for 8–43.5% of total nitrogen export via overland runoff. N lost in dissolved inorganic nitrogen forms (NO ₃ ^– -N + NH ₄ ⁺ -N) accounted for less than 50% of total water associated nitrogen export. Agricultural practices and weather-driven fluctuation in discharge were main reasons for the temporal variations in nutrient losses via stream discharge. Significant correlation between the total nitrogen concentration and stream discharge load was observed. Simple regression models could give satisfactory results for prediction of the total nitrogen concentrations in stream water and can be used for better quantifying nitrogen losses from arable land. Nitrogen losses from the studied watershed via stream discharge during rice season in the year 2002 were estimated to be 10.5 kg N/ha using these simple models.     

A study on the landfill leachate and its impact on the groundwater quality of the greater area

Characterisation of the leachate originating from the Ano Liosia landfill (situated in Attica region, Greece) as well as assessment on the quality of the local aquifer were carried out. The experimental results showed that most of the parameters examined in the leachate samples such as colour, conductivity, TS, COD, NH₃–N, PO₄–P, SO₄ ^2–, Cl^–, K⁺, Fe and Pb were found in high levels. The organic load was quite high since the COD concentrations were in the range of 3250–6125mgL^–1. In addition, the low BOD/COD ratio (0.096–0.195), confirmed that the majority of this organic matter is not easily biodegradable. The groundwater near the landfill site was characterised as not potable and not suitable for irrigation water, since most of the physical and chemical parameters examined – such as colour, conductivity, DS, hardness, Cl^–, NH₃–N, COD, K⁺, Na⁺, Ca²⁺, Fe, Ni and Pb exceeded the permissible limits given by EE, EPA and the Greek Ministry of Agriculture. Furthermore, this study presents the application of the hydrologic evaluation of landfill performance (HELP) model for the determination of the yearly leakage from the base of the landfill after the final capping.     

The effect of selenium on fluoride — clay interactions: Possible environmental health implications

Previous epidemiological studies have shown that dental fluorosis is endemic in the lowland, dry zone of Sri Lanka, which is considered to be an area in which excessive quantities of fluorides are present in the drinking water supplies. It has been found that kaolinitic clay forms a suitable raw material in the defluoridation of water.It is shown that there is a noticeable effect of selenium and media pH on the reactions involved in the interaction of fluoride with clay. In this study, 1 mM fluoride solutions containing SeO ₃ ^2– (selenite) concentrations of 0 mM, 0.1 mM, 0.5 mM and 1 mM were used in the reactions with kaolinitic clay. The effect of pH was monitored in the range 4 to 8. It was observed that fluoride adsorption was maximum at a pH of 5.6 without either SeO ₃ ^2– or SeO ₄ ^2– , the adsorption capacity being 15.2 mol F^– g^–1 clay. However, when the SeO ₃ ^2– concentration was increased up to 0.5 mM at this optimum pH, the adsorption capacity reduced to 12.8 mol F^– g^–1 clay. Monitoring of the effect of SeO ₄ ^2– and media pH on fluoride adsorption showed that when the SeO ₄ ^2– concentration increases from zero to 0.1 mM, there is a reduction of fluoride adsorption capacity. However, when the SeO ₄ ^2– concentration is further increased from 0.1 mM to 1.0 mM, there was an increase in the fluoride adsorption capacity, indicating a more consistent effect of SeO ₃ ^2– on fluoride-kaolinitic clay interaction than SeO ₄ ^2– .Fluoride concentrations in drinking water supplies have a marked effect on dental health and the geochemistry of selenium appears to play an important role in the geochemical mobility of fluoride ions.     

Interactive accumulation of mercury and selenium in the sea starAsterias rubens

Interactions between mercury and selenium accumulation and subcellular binding inAsterias rubens (L.), collected in 1987 from Lille Bælt at Middelfart, Funen, Denmark, were investigated in laboratory experiments. Sea stars exposed to 10µg Hg l^–1 for 30 d accumulated mercury in body wall, tube feet and stomach linearly with time at 1.2, 1.2 and 0.5µg Hg g^–1 dry wt d^–1, respectively. Mercury was accumulated in pyloric caeca and coelomic fluid initially at 1.4µg Hg g^–1 dry wt d^–1 and 9.4 ng Hg ml^–1 d^–1, respectively; after 10 d uptake rates decreased. Sea stars exposed to 75µg Se-SeO ₃ ^{- -} l^–1 accumulated selenium linearly with time over 30 d in the stomach, pyloric caeca, tube feet and body wall at 2.0, 1.2, 1.2 and 0.6µg Se g^–1 dry wt d^–1. Sea stars exposed to 75µg Se-SeO ₄ ^{- -} l^–1 maintained selenium levels in the coelomic fluid at 75µg Se l^–1 over 30 d. Exposure to selenate did not alter the selenium concentrations in the tissues. Sea stars exposed concurrently to 75µg Se-SeO ₃ ^{- -} and 10µg Hg l^–1 accumulated more mercury and selenium in tube feet and body wall than did sea stars exposed to the two elements alone. In pyloric caeca and stomach concurrent exposure reduced accumulation of both elements. Mercury was bound predominantly in the insoluble fraction of the tissues, and soluble mercury was bound in proteins of high (> 70 kilodaltons) or very low (< 6000 daltons) molecular weight. Ca. half of the selenium recovered was bound in the insoluble fraction, and soluble selenium was bound in proteins of high (> 70 kilodaltons) or very low (< 6000 daltons) molecular weight. Interaction between the two elements was exerted predominantly in the insoluble fraction of the tissues.     

Respiration rate and cost of swimming for Antarctic krill,<Emphasis Type="Italic"> Euphausia superba</Emphasis>, in large groups in the laboratory

Constructing realistic energy budgets for Antarctic krill, Euphausia superba, is hampered by the lack of data on the metabolic costs associated with swimming. In this study respiration rates and pleopod beating rates were measured at six current speeds. Pleopod beating rates increased linearly with current speed, reaching a maximum of 6 beats s^–1 at 17 cm s^–1. There was a concomitant linear increase in respiration rate, from 1.8 mg O₂ g_D^–1 h^–1 at 3 cm s^–1 to 8.0 mg O₂ g_D^–1 h^–1 at 17 cm s^–1. The size of the group tested (50, 100 and 300 krill) did not have a significant effect on pleopod beating rates or oxygen consumption (ANCOVA, F=0.264; P>0.05). The cost of transport reached a maximum of 75 J g^–1 km^–1 at 5 cm s^–1, and then decreased with increasing current speed to 29 J g^–1 km^–1. When considered in light of energy budgets for E. superba, these data indicate that the cost of swimming could account for up to 73% of total daily metabolic expenditure during early summer.Communicated by G.F. Humphrey, Sydney     

Seasonal variations of organic-carbon and nutrient transport through a tropical estuary (Tsengwen) in southwestern Taiwan

This paper reports the fluvial fluxes and estuarine transport of organic carbon and nutrients from a tropical river (Tsengwen River), southwestern Taiwan. Riverine fluxes of organic carbon and nutrients were highly variable temporally, due primarily to temporal variations in river discharge and suspended load. The sediment yield of the drainage basin during the study period (1995–1996, 616 tonne km^–2 year^–1) was ca. 15 times lower than that of the long-term (1960–1998) average (9379 tonne km² year^–1), resulting mainly from the damming effect and historically low record of river water discharge (5.02 m³ s^–1) in 1995. The flushing time of river water in the estuary varied from 5 months in the dry season to >4.5 days in the wet season and about 1 day in the flood period. Consequently, distributions of nutrients, dissolved organic carbon (DOC) and particulate organic carbon (POC) were of highly seasonal variability in the estuary. Nutrients and POC behaved nonconservatively but DOC behaved conservatively in the estuary. DOC fluxes were generally greater than POC fluxes with the exception that POC fluxes considerably exceeded DOC fluxes during the flood period. Degradation of DOC and POC within the span of flushing time was insignificant and may contribute little amount of CO₂ to the estuary during the wet season and flood period. Net estuarine fluxes of nutrients were determined by riverine fluxes and estuarine removals (or additions) of nutrients. The magnitude of estuarine removal or addition for a nutrient was also seasonally variable, and these processes must be considered for net flux estimates from the river to the sea. As a result, nonconservative fluxes of dissolved inorganic phosphorus (DIP) from the estuary are –0.002, –0.09 and –0.59 mmol m^–2 day^–1, respectively, for dry season, wet season and flood period, indicating internal sinks of DIP during all seasons. Due to high turbidity and short flushing time of estuarine water, DIP in the flood period may be derived largely from geochemical processes rather than biological removal, and this DIP should not be included in an annual estimate of carbon budget. The internal sink of phosphorus corresponds to a net organic carbon production (photosynthesis–respiration, p–r) during dry (0.21 mmol m^–2 day^–1) and wet (9.5 mmol m^–2 day^–1) seasons. The magnitude of net production (p–r) is 1.5 mol m^–2 year^–1, indicating that the estuary is autotrophic in 1995. However, there is a net nitrogen loss (nitrogen fixation–denitrification < 0) in 1995, but the magnitude is small (–0.17 mol m^–2 year^–1).     

Benthic oxygen uptake and carbon cycling under aphotic and resource-limiting conditions in a submarine cave

To establish relationships between organic input to the benthos and decreases in benthic population biomass and density, benthic oxygen uptake was measured in an oligotrophic submarine cave in the northwestern Mediterranean Sea (Marseille, France), on seven separate occasions in 1987, using an in situ bell-jar respirometer. Oxygen uptake was measured in both the outer twilight section and the dark inner section of the cave during an annual survey (seven recording periods from February 1987 to November 1988). The mean annual benthic oxygen uptake was 80.9 litres O₂ m^–2 yr^–1 for the twilight outer section and 15.5 litres O₂ m^–2 yr^–1 for the dark inner section. The results are discussed and the biogeochemical budget for particulate organic carbon at the sediment-water interface calculated. Respiration rates (expressed as carbon equivalents), together with previously published data on vertical fluxes and burial of organic carbon, revealed that anaerobic pathways accounted for 14% and aerobic pathways for 86% of the total benthic metabolism in the outer part of the cave. In the inner section of the cave, degradation of organic carbon occurred only through aerobic degradation, indicating a strongly carbon-limited ecosystem. The low respiration rates recorded in the dark section were similar to values recorded for some oligotrophic deep-sea environments (1 000 to 2 000 m). Such budgets are essential preliminary steps in order to accurately model benthic metabolic pathways. The determination of annual fluxes linked to the acquisition of long-term data will yield better knowledge of the recycling processes at the water-sediment interface.     

Optimum Nitrogen Use and Reduced Nitrogen Loss for Production of Rice and Wheat in the Yangtse Delta Region

A long-term field and lysimeter experiment under different amount of fertilizer-N application was conducted to explore the optimal N application rates for a high productive rice–wheat system and less N leaching loss in the Yangtse Delta region. In this region excessive applications of N fertilizer for the rice–wheat production has resulted in reduced N recovery rates and environment pollution. Initial results of the field experiments showed that the optimal N application rate increased with the yield. On the two major paddy soils (Hydromorphic paddy soil and Gleyed paddy soil) of the region, the optimal N application rate was 225–270 kg N hm^–2 for rice and 180–225 kg N hm^–2 for wheat, separately. This has resulted in the highest number of effective ears and Spikelets per unit area, and hence high yield. Nitrogen leaching in the form of NO ₃ ^– -N occurs mainly in the wheat-growing season and in the ponding and seedling periods of the paddy field. Its concentration in the leachate increased with the N application rate in the lysimeter experiment. When the application rate reached 225 kg N hm^–2, the concentration rose to 5.4–21.3 mgN l^–1 in the leachate during the wheat-growing season. About 60% of the leachate samples determined contained NO ₃ ^– -N beyond the criterion (NO ₃ ^– -N 10 mg l^–1) for N pollution. In the field experiment, when the N application rate was in the range of 270–315 kg hm^–2, the NO ₃ ^– -N concentration in the leachate during the wheat-growing season ranged from 1.9 to 11.0 mg l^–1. About 20% of the leachate samples reached close to, and 10% exceeded, the criterion for N pollution. Long-term accumulation of NO ₃ ^– -N from leaching will no doubt constitute a potential risk of N contamination of the groundwater in the Yangtse Delta Region.     

Hydrochemical Monitoring and Heavy Metal Contaminations at the Narim Mine Creek in the Sulcheon District, Republic of Korea

The Narim gold mine is located approximately 200km southeast of Seoul within the Sulcheon mineralised district in the Yeongnam massif, Korea. In this study, environmental geochemical analyses were undertaken for soil, sediment and water samples collected in April, September and November in 1998 from the Narim mine creek. The mine area consists mainly of granitic gneiss; however, mineral constituents of soil and sediment near the mine were mainly composed of quartz, feldspar, mica, amphibole, some pyrite and clay minerals. Also were found some pyrite, arsenopyrite, chalcopyrite, sphalerite, galena, malachite, goethite, various hydroxide and unidentified secondary minerals. Generally, high concentrations of heavy metals in the soil and sediment are correlated with a high proportion of secondary minerals. Hydrochemical compositions of water samples are characterised by relative significant enrichment of Na⁺+K⁺ and alkali metals in the ground water, whereas the surface and mine waters are relatively enriched in Ca²⁺+Mg²⁺ and heavy metals. Anion contents of the ground waters are typically enriched in HCO₃ ^–, NO₃ ^– and Cl^–, whereas the surface and mine waters are highly enriched in HCO₃ ^– and SO₄ ^2–. The pH and EC values of the surface water from the non-mine creek are relatively lower compared with those of the surface water around the mine and waste dump. The range of D and ¹⁸O values (d parameters) of the water samples are shown in distinct two groups for the April waters of 10.1–13.1, and for the November waters of 5.8–7.9, respectively. This range variation indicates that two group water were composed of distinct waters because of seasonal difference. Geochemical modelling showed that mostly heavy toxic metals may exist largely in the form of free metal (M²⁺) and metal-sulphate (MSO₄ ^2–), and SO₄ ^2– concentration influenced the speciation of heavy metals in the mine water. These metals in the ground water could be formed of CO₃ ^– and OH^– complex ions. Using a computer program, saturation indices of albite, calcite, dolomite in mostly surface water show undersaturated and progressively evolved toward the saturation state, however, ground and mine waters are nearly saturated. The gibbsite, kaolinite and smectite are supersaturated in the surface and ground water, respectively. Calculated water-mineral reaction and stabilities suggest that the weathering of silicate minerals may be stable kaolinite. The clay minerals of K-illite and Na-smectite will be transformed to more stable kaolinite owing to the continuous reaction.     

Atmospheric Deposition, Mineralization and Leaching of Nitrogen in Subtropical Forested Catchments, South China

In recent years, China has conducted considerable research focusing on the emission and effects of sulphur (S) on human health and ecosystems. By contrast, there has been little emphasis on anthropogenic nitrogen (N) so far, even though studies conducted abroad indicate that long-range atmospheric transport of N and ecological effects (e.g. acidification of soil and water) may be significant. The Sino-Norwegian project IMPACTS, launched in 1999, has established monitoring sites at five forest ecosystems in the southern part of PR China to collect comprehensive data on air quality, acidification status and ecological effects. Here we present initial results about N dynamics at two of the IMPACTS sites located near Chongqing and Changsha, including estimation of atmospheric deposition fluxes of NO_x and NH_x and soil N transformations. Nitrogen deposition is high at both sites when compared with values from Europe and North America (25–38 kg ha^–1 yr^–1). About 70% of the deposited N comes as NH₄, probably derived from agriculture. Leaching of N from soils is high and nearly all as NO₃ ^–1. Transformation of N to NO₃ ^–1 in soils results in acidification rates that are high compared to rates found elsewhere. Despite considerable leaching of NO₃ ^–1 from the root zone of the soils, little NO₃ ^–1 appears in streamwater. This indicates that N retention or denitrification, both causing acid neutralization, may be important and probably occur in the groundwater and groundwater discharge zones. The soil flux density of mineral N, which is the sum of N deposition and N mineralization, and which is dominated by the N mineralization flux, may be a good indicator for leaching of NO₃ ^–1 in soils. However, this indicator seems site specific probably due to differences in land-use history and current N requirement.     

Chemical Changes in Agricultural Soils of Korea: Data Review and Suggested Countermeasures

The monitoring of chemical properties, including heavy metals, in soils is necessary if better management and remediation practices are to be established for polluted soils. The National Institute of Agricultural Science and Technology initiated a monitoring study that investigated fertility and heavy metal contents of the benchmarked soils. The study covered paddy soils, upland soils, and horticultural soils in the plastic film houses, and orchard soils throughout the Korea from 1990 to 1998. Likewise,4047 samples of paddy and 2534 samples of plastic house in 1999 and 2000 were analyzed through the Soil Environment Conservation Act. Soil chemical properties such as pH, organic matter, availablephosphate and extractable calcium, magnesium and potassium contents, and heavy metal contentssuch as cadmium, copper, lead, zinc, arsenic, mercury, and cobalt contents were analyzed. The studyshowed that the average contents of organic matter, available phosphate, and extractable potassiumrapidly increased in plastic house soils than in upland or paddy soils. Two kinds of fertilizer recommendation systems were established for the study: the standard levels by national soil average data for 77 crops and the recommendation by soil test for 70 crops. Standard nitrogen fertilizer application levels for cereal crops changed from 94 kg/ha in 1960s, 99 kg/ha in 1970s, 110 kg/ha in 1980s to 90 kg/ha in 1990s. The K₂O-fertilizer also changed from 67 kg/ha in 1960s, 76 kg/ha in 1970s, 92 kg/ha in 1980s, andonly 44 kg/ha in 1990s. In rice paddy fields, the average contents of Cd, Cu, Pb, and Zn in surface soils(0–15 cm depth) were 0.11 mg kg^–1(ranged from 0 to 1.01), 4.70 mg kg^–1(0–41.59), 4.84 mg kg^–1(0–66.44), and 4.47 mg kg^–1(0–96.70), respectively. In the uplands, the average contents of Cd, Cu, Pb, Zn,and As in surface soils (0–15 cm depth) were 0.135 mg kg^–1(ranged from 0 to 0.660), 2.77 mg kg^–1(0.07–78.24), 3.47 mg kg^–1(0–43.00), 10.70 mg kg^–1(0.30–65.10), and 0.57 mg kg^–1(0.21–2.90), respectively. In plastic film houses, the average contents of Cd, Cu, Pb, Zn, and As in surface soil were 0.12 mg kg^–1(ranging from 0 to 1.28), 4.82 mg kg^–1(0–46.50), 2.68 mg kg^–1(0–46.50), 31.19 mg kg^–1(0.19–252.0), and 0.36 mg kg^–1(0–4.98), respectively. In orchard fields, the averagecontents of Cd, Cu, Pb, Zn, As, and Hg in surface soils (0–20 cm depth) were 0.11 mg kg^–1(ranged from 0–0.49), 3.62 mg kg^–1(0.03–45.30), 2.30 mg kg^–1(0–27.80), 16.60 mg kg^–1(0.33–105.50),0.44 mg kg^–1(0–4.14), and 0.05 mg kg^–1(0.01–0.54), respectively. For polluted soils with over thewarning content levels of heavy metals, fine red earth application, land reconsolidation and soilamelioration such as lime, phosphate, organic manure, and submerging were recommended. For the countermeasure areas, cultivation of non-edible crops such as garden trees, flowers, and fiber crops; landreformation; and heavy application of finered earth (up to 30 cm) were strongly recommended. Landuse techniques should be changed to beharmonious with the environment to increase yield andincome. Soil function characteristics should betaken into account.     

Influence of fertilizer and sewage sludge compost on yield and heavy metal accumulation by lettuce grown in urban soils

Previous research has demonstrated that many urban soils are enriched in Pb, Cd and Zn. Culture of vegetable crops in these soils could allow transfer of potentially toxic metals to foods. Tanya lettuce (Lactuca sativa L.) was grown in pots of five urban garden soils and one control agricultural soil to assess the effect of urban-soil metal enrichment, and the effect of soil amendments, on heavy metal uptake by garden vegetables. The amendments included NPK fertilizer, limestone, Ca(H₂PO₄)₂, and two rates of limed sewage sludge compost. Soil Cd ranged from 0.08 to 9.6 mg kg^–1; soil Zn from 38 to 3490 mg kg^–1; and soil Pb from 12 to 5210 mg kg^–1. Lettuce yield on the urban garden soils was as great as or greater than that on the control soil. Lettuce Cd, Zn and Pb concentrations increased from 0.65, 23, and 2.2 mg kg^–1 dry matter in the control soil to as high as 3.53, 422 and 37.0 mg kg^–1 on the metal-rich urban garden soils. Adding limestone or limed sewage sludge compost raised soil pH and significantly reduced lettuce Cd and Zn, while phosphate fertilizer lowered soil pH and had little effect on Zn but increased Cd concentration in lettuce. Urban garden soils caused a significant increase in lettuce leaf Pb concentration, especially on the highest Pb soil. Adding NPK fertilizer, phosphate, or sludge compost to two high Pb soils lowered lettuce Pb concentration, but adding limestone generally did not. On normally fertilized soils, Pb uptake by lettuce was not exceptionally high until soil Pb substantially exceeded 500 mg kg^–1. Comparing garden vegetables and soil as potential sources of Pb risk to children, it is clear that the risk is greater through ingestion of soil or dust than through ingestion of garden vegetables grown on the soil. Urban dwellers should obtain soil metal analyses before selecting garden locations to reduce Pb risk to their children.     

Response of the microbial food web to manipulation of nutrients and grazers in the oligotrophic Gulf of Aqaba and northern Red Sea

The control mechanisms within the pelagic microbial food web of the oligotrophic Gulf of Aqaba and the northern Red Sea were investigated in the spring of 1999. Nutrient conditions and potential grazer impact were manipulated in a series of dilution experiments. Ambient nutrient concentrations and autotrophic biomass were very low (0.23–1.21 µmol NO₃ l^–1, 0.06–0.98 µmol NH₄ l^–1, 1.08–1.17 µmol Si l^–1, 0.08–0.12 µmol P l^–1, 0.15–0.36 µg chlorophyll a l^–1). The planktonic community was characterized by low abundances [3.0–5.5×10⁵ heterotrophic bacteria ml^–1, 0.58–7.2×10³ ultraphytoplankton <8 µm ml^–1 (small eukaryotic photoautotrophs and Prochlorococcus sp., excluding Synechococcus sp.), 0.45–4.4×10⁴ Synechococcus sp. ml^–1, 0.32–1.2×10³ heterotrophic nanoflagellates ml^–1, 1.3–3.8×10³ phytoplankton >8 µm l^–1, 0.93–5.4×10² microzooplankton l^–1] and dominated by small forms (0.2–8 µm). Dinoflagellates and oligotrichous ciliates were the most common groups in initial samples among the phytoplankton >8 µm and microzooplankton, respectively. Results show that bottom-up and top-down control mechanisms operated simultaneously. Small organisms were vulnerable to grazing, with maximum grazing rates of 1.1 day^–1 on heterotrophic bacteria and 1.3 day^–1 on ultraphytoplankton. In contrast, algae >8 µm showed stronger signs of nutrient limitation, especially when the final assemblages were dominated by diatoms. Synechococcus sp. were not grazed and only showed moderate to no response to nutrient additions. The high spatial and temporal variation of our results indicates that the composition of the planktonic community determines the prevailing control mechanisms. It further implies that, at this transitional time of the year (onset of summer stratification), the populations fluctuate about an equilibrium between growth and grazing.Communicated by O. Kinne, Oldendorf/Luhe