Comparative chronic toxicity of nanoparticulate and ionic zinc to the earthworm Eisenia veneta in a soil matrix

Manufactured nanoparticles (NPs) are increasingly being used in a range of consumer products and are already entering the environment. NP ZnO is one of the most widely used and potentially toxic NPs in aquatic exposures. It is likely that ZnO nanoparticles will also be bioavailable to soil organisms, studies on ZnO NP toxicity in a soil matrix are lacking. We exposed the earthworm Eisenia veneta to uncoated NP ZnO (<100 nm) dosed to soil and food at 250 and 750 mg Zn kg(-1) for 21 d. Concurrent exposures of equivalent ionic Zn were conducted with ZnCl(2) and for both forms effects on life history traits, immune activity and Zn body concentrations were compared. Despite slightly higher measured body concentrations, NP ZnO generally had less impact than ZnCl(2) on measured traits. At 750 mg Zn kg(-1), reproduction declined by 50% when exposed to NP ZnO but was almost completely inhibited by ZnCl(2). Similarly, immune activity was unaffected by NP ZnO but was suppressed by 20% when exposed to ZnCl(2). Scanning electron microscopy analysis of worm tissues following 24h aqueous exposure showed the presence of ZnO particles suggesting that NPs can be taken up in particulate form. This may explain the reduced effects at similar body concentrations seen in the soil study. Our findings suggest that risk assessments do not need to go beyond considering the metal component of NP ZnO in soils at least for the larger size uncoated particles considered here.     

Characterisation of NOM by adsorption parameters and effective diffusivities

Adsorption equilibria were studied with RO isolates for both activated carbon and activated alumina. Maximum carbon loadings on the order of 65 mg/g DOC were obtained, while the maximum loadings of activated alumina were about 30 mg/g DOC. In the latter case the slope of the isotherms was generally steeper, indicating weaker adsorbabilities of some of the NOM compounds on the metal oxide adsorbent. Since NOM must be regarded as a multi-component system with respect to adsorption, the data were evaluated by the adsorption analysis procedure. The results were used for a theoretical comparison of NOM adsorption based on the same initial concentration of all samples. The method of colloidal titration was applied to the RO isolates in the range pH = 3–8. Poly-DADMAC was used as a cationic polymer, and a streaming current instrument was used for end point detection. The results which are termed anionic colloidal charge (ACC) values increase with increasing pH for pH = 3–6 while they are about constant for pH = 6–8. At the samples' original pH, the specific ACC values found range from 5.2 to 7.6 meq/g DOC. Mass transfer coefficients for NOM adsorption on granular activated carbon were determined for both RO and EVAP isolates, respectively. The data were used to derive effective diffusivities for each sample. The results differ by a factor of about 2 with the Maridalsvann sample having the highest and the Humex sample having the lowest diffusivity. Furthermore, the results for the EVAP isolates are in 8 of 9 cases higher than for the RO samples. Based on a comparison with known macromolecules, average molecular weight values were estimated to be on the order of 700–4800 Dalton.     

Toxicity of zinc oxide nanoparticles in the earthworm, Eisenia fetida and subcellular fractionation of Zn

The extensive use of nanoparticles (NPs) in a variety of applications has raised great concerns about their environmental fate and biological effects. This study examined the impact of dissolved organic matter (DOM) and salts on ZnO NP dispersion/solubility and toxicity to the earthworm Eisenia fetida. To be able to better evaluate the toxicity of NPs, exposure in agar and on filter paper was proposed for enabling a comparison of the importance of different uptake routes. A dose-related increase in mortality was observed in earthworms exposed in agar with almost 100% mortality after 96 h exposure to the highest concentration (1000 mg ZnO/kg agar). Scanning electron microscopy (SEM) showed that the addition of salts enhanced the aggregation of ZnO NPs in agar and consequently affected the dissolution behavior and biological availability of the particles. On filter paper, mortality was the highest at the lowest exposure concentration (50 mg ZnO/L) and seemed to decrease with increasing exposure levels. TEM images of ZnO showed that the solubility and morphology of NPs were changed dramatically upon the addition of humic acids (HA). The subcellular distribution pattern of Zn in earthworms after 96 h exposure in agar and on filter paper showed that the Zn taken up via dietary ZnO particles (from agar) was mainly found in organelles and the cytosol while the Zn accumulated as soluble Zn from filter paper was mainly distributed in cell membranes and tissues. Antioxidant enzymatic activities (SOD, CAT, and GSH-px) were investigated in the worms surviving the toxicity tests. A slight increase of SOD activities was observed at the lowest exposure dose of ZnO (50mg/kg), followed by a decrease at 100mg/kg in the agar cubes. Activities of both CAT and GSH-Px enzymes were not significantly influenced in the worms exposed to agar, although a slight decrease at 500 and 1000 mg ZnO/kg agar was observed. A similar change trend of SOD activities was observed for the earthworms on filter paper, but a significant decrease began at a higher ZnO NP concentration of 500 mg ZnO/L. The use of soil extracts instead of deionized water (DW) to simulate a realistic exposure system significantly reduced the toxicity of the ZnO NPs on filter paper, which increases the predictive power of filter paper toxicity tests for the environmental risk assessment of NPs.     

Silver nanoparticles: behaviour and effects in the aquatic environment

This review summarises and evaluates the present knowledge on the behaviour, the biological effects and the routes of uptake of silver nanoparticles (Ag NPs) to organisms, with considerations on the nanoparticle physicochemistry in the ecotoxicity testing systems used. Different types of Ag NP syntheses, characterisation techniques and predicted current and future concentrations in the environment are also outlined. Rapid progress in this area has been made over the last few years, but there is still a critical lack of understanding of the need for characterisation and synthesis in environmental and ecotoxicological studies. Concentration and form of nanomaterials in the environment are difficult to quantify and methodological progress is needed, although sophisticated exposure models show that predicted environmental concentrations (PECs) for Ag NPs in different environmental compartments are at the range of ng L(-1) to mg kg(-1). The ecotoxicological literature shows that concentrations of Ag NPs below the current and future PECs, as low as just a few ng L(-1), can affect prokaryotes, invertebrates and fish indicating a significant potential, though poorly characterised, risk to the environment. Mechanisms of toxicity are still poorly understood although it seems clear that in some cases nanoscale specific properties may cause biouptake and toxicity over and above that caused by the dissolved Ag ion. This review concludes with a set of recommendations for the advancement of understanding of the role of nanoscale silver in environmental and ecotoxicological research.     

Capillary zone electrophoretic studies on Norwegian surface water natural organic matter

Capillary zone electrophoresis (CZE) is a useful tool for the analysis of the electrophoretic behavior of anionic polyelectrolytes like humic substances. CZE was used to compare natural organic matter (NOM) with high ash content obtained by reverse osmosis (RO) and low temperature, low pressure evaporation (Ev.) from different Norwegian surface water sources. The quantitative relation between the resulting electrophoretic signals (peak height and area) and the carbon amount of the injected NOM samples was found linear. The NOM gave homogeneous signals in CZE, with a distribution of the detection signals around an average electrophoretic mobility (AEM) corresponding to the charge density distribution of the NOM, governed by the distribution of their molecular sizes and acidities. Like humic substances, NOM only appears as anions in capillary electrophoresis (CE), but the high ash content of these samples and the presence of metals strongly influenced their mobilities at lower pH. CZE could be used as a tool for the rapid evaluation of the average net charge and the molecular radius of the NOM at pH 5.1.     

Ecotoxicological effects of an aged TiO2 nanocomposite measured as apoptosis in the anecic earthworm Lumbricus terrestris after exposure through water, food and soil

Titanium dioxide nanoparticles seem to have a low toxicity to terrestrial organisms, though few studies are published in this area. TiO(2) used in sunscreens are nanocomposites where TiO(2) has been coated with magnesium, silica or alumina, as well as amphiphilic organics like polydimethyl siloxane (PDMS), and these coatings are modified by ageing. We assessed the ecotoxicity and propensity for bioaccumulation of an aged TiO(2) nanocomposite used in sunscreen cosmetics, and its potential effect on the frequency of apoptosis in different earthworm tissues. The earthworm Lumbricus terrestris was exposed to the TiO(2) nanocomposite for 7 days in water or 2-8 weeks in soil with the nanocomposite mixed either into food or soil at concentrations ranging from 0 to 100 mg kg(-1). Apoptosis was then measured by immunohistochemistry and Ti localized by XRF microscopy. Results showed no mortality, but an enhanced apoptotic frequency which was higher in the cuticule, intestinal epithelium and chloragogenous tissue than in the longitudinal and circular musculature. TiO(2) nanoparticles did not seem to cross the intestinal epithelium/chloragogenous matrix barrier to enter the coelomic liquid, or the cuticule barrier to reach the muscular layers. No bioaccumulation of TiO(2) nanocomposites could thus be observed.     

Biological vs. chemical properties of natural organic matter isolated from selected Norwegian lakes

Relationships among different spectroscopic, chemical, and biological properties of dissolved natural organic matter (NOM) were investigated. NOM samples were isolated by means of reverse osmosis from eight Norwegian lakes. Elemental composition, absorption spectra (UV, VIS, IR), the influence on algal growth, and accumulation rates of metals by mussels in the presence of NOM were measured. Linear regression and principal components analyses were utilised to assess relationships between the biological and chemical properties. It was concluded that the content of organic matter in the isolates and the aromaticity of NOM, as characterised by UV and VIS spectra, are best correlated with the biological properties.     

Characterization of natural organic matter from eight Norwegian surface waters: Proton and copper binding

As a part of the International NOM-Typing Project, proton and copper binding studies were conducted on ultrafiltered (>1000 dal.) and dialysed (>100 dal.) natural organic matter (NOM) samples from eight Norwegian Lakes. The NOM samples were similar with respect to proton and copper binding, although minor differences were observed among the samples of different origin. Slight variations occurred for seasonal changes and lime additions. The proton binding pK_a values grouped in three distinct classes: pK_a1 = 4.20–4.28; pK_a2 = 6.61–6.87; and pK_a3 = 9.27–9.8. The average total proton binding site concentration of the NOM samples was: 12.7 meq/g total organic carbon (TOC). Two binding sites were established for copper with average log K1 = 4.84 and log K2 = 7.17. The average site concentration for samples isolated by reverse osmosis (RO) was 0.56 μmol/mg C. Copper binding characteristics appear to be influenced by the method of sample isolation. For NOM isolated by low pressure evaporation (evap), binding site concentrations are smaller, conditional stability constants are higher, variability of the copper complexation capacity is smaller, and correlation with elemental composition (C, N, H) is better than in the case of NOM isolated by RO.     

Occurrence and degradation of butyltins and wastewater marker compounds in sediments from Barcelona harbor, Spain

Contamination of Barcelona harbor sediments was assessed by the quantitative determination of butyltins (TBT, DBT and MBT) and surfactant intermediates, namely linear alkylbenzenes (LABs) and nonylphenols (NPs), as markers of urban and industrial wastewater contamination, respectively. Degradation indexes of TBT and LABs were calculated. Tributyltin predominated in the whole area over its degradation products, ranging from 98 to 4702 ng Sn/g. These elevated concentrations reveal a persistent historical contamination and a moderate degradation (BT(deg)). Moreover, the high LAB concentrations (1.2-53.1 microg/g) compared to the relatively low NP levels (3.8-72.0 ng/g) suggest a predominance of urban over industrial wastewater inputs, although a significant correlation (r(2) = 0.82, N = 12, P = 0.001) between LABs and NPs was found. Stormwater runoff and combined sewer overflows (CSO) were likely the most possible sources for both surfactant intermediates. The high degradation index values obtained for LABs could indicate an improvement in the wastewater management reducing its recent discharge into the Barcelona harbor area.     

Transport of NOM and trace metals through macropores in the Lake Skjervatjern catchment

In the dystrophic Lake Skjervatjern, located at the west coast of Norway, periods with high precipitation coincide with an increase in the concentrations of natural organic matter (NOM) and several trace elements. The lake has no visual inlets, and, during high flow periods, a major part of the drainage follows macropores, entering the lake 10–40 cm below the surface. Water from the lake and the macropores were fractionated according to size by means of a hollow fiber ultra-filtration technique, during two periods with high precipitation. In the macropores, the high molecular weight form of NOM (nominal molecular cut off > 10 kDa) appears to be an important transporting agent for several trace elements that strongly interact with NOM (e.g., Fe, Al, Pb, Sm, La, Ce, and Eu). In contrast, anionic (V and As) and acid sensitive (Mn and Cs) elements were, generally, at a low molecular weight form (nominal molecular cut off < 3 kDa). The latter showed similar or lower concentrations in the macropores compared to the lake water, and NOM were apparently of small importance as a carrier for V, As, Mn, and Cs. Differences in concentration and size distribution of trace elements between the macropores and the lake basins indicate that parts of NOM and associated trace elements that enter the lake in a high molecular weight form, undergo aggregation and gravitational settling and thereby become a part of the lake sediments.     

Changes of AhR-mediated activity of humic substances after irradiation

Humic substances (HS) and natural organic matter (NOM) are natural organic compounds ubiquitous in the environment. However, some studies indicate that both HS and NOM can act as xenobiotics, e.g. induce hormone-like effects in fish, amphibians and invertebrates. Molecules of these substances contain a number of aromatic rings and conjugated double bonds--the so called chromophores. Irradiation of dissolved HS and NOM can lead to a series of photochemical reactions which can act on these substances itself, or on other substances present in aquatic environment along with HS and NOM such as e.g. xenobiotics. In our previous study, we have found significant interactions of five humic acids (HA) with cytosolic aryl hydrocarbon receptor (AhR) in an in vitro bioassay based on H4IIE-luc cells. In the present study, we have studied the changes in AhR-mediated activities both of HS and NOM after irradiation that simulated natural solar light. Nine different HS and two NOM samples were irradiated in Pyrex tubes with a medium-pressure mercury lamp for a duration of 0 to 52 h (which corresponds to 0-52 d natural solar radiation). Original concentrations of the samples were 50 mg L(-1), and the greatest concentration of HS and NOM photoproducts subsequently tested in the bioassay was 17 mg L(-1), which is an environmentally relevant concentration. After irradiation the absorbances of all the samples were less than the original materials. The AhR-mediated activity of the HA-Fluka and HA Sodium Salt were partially decreased by irradiation. The activities of other HS and NOM, that were either AhR-active or -inactive were not changed by irradiation. The results of the study demonstrate that AhR-mediated activities of two active HA is caused by both photo-stable and photo-labile AhR activators, while the other three active HA contain only photo-stable AhR activators. Potential mechanisms of the observed irradiation-induced changes in AhR-mediated activities are discussed.     

Environmental fate of alkylphenols and alkylphenol ethoxylates--a review

Alkylphenol ethoxylates (APEs) are widely used surfactants in domestic and industrial products, which are commonly found in wastewater discharges and in sewage treatment plant (STP) effluents. Degradation of APEs in wastewater treatment plants or in the environment generates more persistent shorter-chain APEs and alkylphenols (APs) such as nonylphenol (NP), octylphenol (OP) and AP mono- to triethoxylates (NPE1, NPE2 and NPE3). There is concern that APE metabolites (NP, OP, NPE1-3) can mimic natural hormones and that the levels present in the environment may be sufficient to disrupt endocrine function in wildlife and humans. The physicochemical properties of the APE metabolites (NP, NPE1-4, OP, OPE1-4), in particular the high K(ow) values, indicate that they will partition effectively into sediments following discharge from STPs. The aqueous solubility data for the APE metabolites indicate that the concentration in water combined with the high partition coefficients will provide a significant reservoir (load) in various environmental compartments. Data from studies conducted in many regions across the world have shown significant levels in samples of every environmental compartment examined. In the US, levels of NP in air ranged from 0.01 to 81 ng/m3, with seasonal trends observed. Concentrations of APE metabolites in treated wastewater effluents in the US ranged from < 0.1 to 369 microg/l, in Spain they were between 6 and 343 microg/l and concentrations up to 330 microg/l were found in the UK. Levels in sediments reflected the high partition coefficients with concentrations reported ranging from < 0.1 to 13,700 microg/kg for sediments in the US. Fish in the UK were found to contain up to 0.8 microg/kg NP in muscle tissue. APEs degraded faster in the water column than in sediment. Aerobic conditions facilitate easier further biotransformation of APE metabolites than anaerobic conditions.     

Environmental impact studies of barium and radium discharges by produced waters from the "Bacia de Campos" oil-field offshore platforms,Brazil

Produced water samples from different E&P offshore petroleum platforms, belonging to the Bacia de Campos oil field, Brazil, were analyzed for barium, 226Ra and 'Ra. The concentrations measured are in the range of 0.36-25.7 mg l(-1) for barium, 0.012-6.0 Bq l(-1) for 226Ra and <0.05-12.0 Bq l(-1) for 1Ra. A strong correlation between the concentration of barium and radium isotopes was observed (226Ra: r2=0.926: 228Ra: r2=0.785). Additionally, seawater and sediment samples were taken at different distances (from 250 to 1,000 m) from the two selected platforms. Water samples were analyzed for dissolved and particulate barium, 226Ra and 225Ra and the sediment samples for total and leachable barium, 226Ra and 228Ra. The results showed that even for the shortest sampling distance (250 m) from the discharge point, barium, 226Ra and 228Ra concentrations are similar to the local background, indicating that dispersion by local currents is enough to minimize environmental impacts.     

Distribution characteristics of fluoride and aluminum in soil profiles of an abandoned tea plantation and their uptake by six woody species

Distribution characteristics of fluoride (F) and aluminum (Al) in soil profiles of an abandoned tea plantation in Hong Kong and their uptake by six woody species namely Camellia sinensis, Melastoma affine, Sterculia lanceolata, Ardisia crenata, Acacia formosa and Machilus thunbergii were investigated. C. sinensis accumulated both F (656 mg/kg in the leaves) and Al (8910 mg/kg in the leaves). M. Affine only accumulated Al (9932 mg/kg in the leaves), while S. lanceolata, A. crenata, A. formosa and M. Thunbergii were Al (26-115 mg/kg in the leaves) and F (20-25 mg/kg in the leaves) excluders. Water-soluble F and Al contents accumulated in surface soils (especially 0-3 cm) and decreased with depth along soil profiles: A layers (2.0 +/- 0.6 and 31 +/- 5.8 mg/kg) > B layers (1.5 +/- 0.2 and 27 +/- 3.5 mg/kg) > C layers (1.3 +/- 0.2 and 20 +/- 2.7 mg/kg), respectively. The water-soluble, NH4Ac-extractable and HCl-extractable F in soil profiles were significantly correlated (P < .01). F concentrations in all soil layers (n = 51) of soil profiles (n = 17) were significantly correlated (P < .01) to Al concentrations in terms of water-soluble Al/F, HCl-extractable Al/F and NH4Ac-extractable Al/F, due to the formation of Al-F complexes in soil. F contents extracted with deionized water (pH = 6.68), 1 mol/l HCl and 1 mol/l NH4Ac in soil could be used to predict F concentrations in the leaves, stems and roots of the six plants.     

Physiological effects of nanoparticles on fish: a comparison of nanometals versus metal ions

The use of nanoscale materials is growing exponentially, but there are also concerns about the environmental hazard to aquatic biota. Metal-containing engineered nanoparticles (NPs) are an important group of these new materials, and are often made of one metal (e.g., Cu-NPs and Ag-NPs), metal oxides (e.g., ZnO and TiO(2) NPs), or composite of several metals. The physiological effects and toxicity of trace metals in the traditional dissolved form are relatively well known and the overall aim of this review was to use our existing conceptual framework of metal toxicity in fish to compare and contrast the effects of nanometals. Conceptually, there are some fundamental differences that relate to bioavailability and uptake. The chemistry and behaviour of nanometals involves dynamic aspects of aggregation theory, rather than the equilibrium models traditionally used for free metal ions. Some NPs, such as Cu-NPs, may also release free metal ions from the surface of the particle. Biological uptake of NPs is not likely via ion transporters, but endocytosis is a possible uptake mechanism. The body distribution, metabolism, and excretion of nanometals is poorly understood and hampered by a lack of methods for measuring NPs in tissues. Although data sets are still limited, emerging studies on the acute toxicity of nanometals have so far shown that these materials can be lethal to fish in the mg-μgl(-1) range, depending on the type of material. Evidence suggests that some nanometals can be more acutely toxic to some fish than dissolved forms. For example, juvenile zebrafish have a 48-h LC(50) of about 0.71 and 1.78mgl(-1) for nano- and dissolved forms of Cu respectively. The acute toxicity of metal NPs is not always explained, or only partly explained, by the presence of free metal ions; suggesting that other novel mechanisms may be involved in bioavailability. Evidence suggests that nanometals can cause a range of sublethal effects in fish including respiratory toxicity, disturbances to trace elements in tissues, inhibition of Na(+)K(+)-ATPase, and oxidative stress. Organ pathologies from nanometals can be found in a range of organs including the gill, liver, intestine, and brain. These sublethal effects suggest some common features in the sublethal responses to nanometals compared to metal salts. Effects on early life stages of fish are also emerging, with reports of nanometals crossing the chorion (e.g., Ag-NPs), and suggestions that the nano-forms of some metals (Cu-NPs and ZnO NPs) may be more toxic to embryos or juveniles, than the equivalent metal salt. It remains possible that nanometals could interfere with, and/or stimulate stress responses in fish; but data has yet to be collected on this aspect. We conclude that nanometals do have adverse physiological effects on fish, and the hazard for some metal NPs will be different to the traditional dissolved forms of metals.     

Chemical evaluation of potable water in Eastern Qinghai Province, China: human health aspects

Electric conductivity, pH, COD(Mn), nutrient concentration, chloride and sulfate concentrations, total dissolved sodium, potassium, calcium, magnesium, manganese, iron, cadmium, copper, arsenic, nickel, zinc, chromium and lead were evaluated to clarify concerns about the quality and safety of water used for drinking purposes in Qinghai Province, China. For this purpose, 12 water samples were collected from different villages, Qinghai (Koko Nor) Lake and medicinal springs close to the Town of Pingang during a study visit to China in 2003. The results showed that National Chinese and WHO drinking water standards were exceeded for nutrient concentration (3.2 mg l(-1) of TOT-N and 0.2 mg l(-1) of TOT-P) from Qinghai Lake. The presence of elevated electric conductivity (550 mS m(-1)) in mineral water resort samples should be a matter of a public concern. Also, samples from medicinal springs showed high concentrations of Fe (up to 1.9 mg l(-1)), As (up to 0.1 mg l(-1)) and Ni (0.05 mg l(-1)), which may be detrimental for human health if the water is consumed on a daily basis. The concentrations of Cu, Cd, Cr and Pb did not exceed the National Chinese and WHO drinking water standards, and therefore, water from the sampling area does not pose any significant threat to the consumers' health regarding these metals.     

Unraveling the causes of the toxicity of extremely acid waters of volcanic origin

A river ecosystem in East Java, Indonesia, fed by a volcanic lake with high concentrations of dissolved metals and a low pH, was found to support only few macroinvertebrates. To unravel the causes of toxicity and to determine the level of dilution necessary to obtain non-toxic water, a bioassay was conducted with the fairy shrimp Thamnocephalus platyurus. A partial toxicity identification evaluation (TIE) approach was used with EDTA as a chelating agent to relate toxicity to pH and metal concentrations. Three water samples were tested, with pHs ranging from 0.72 to 4.5, and diluted with water from a neutral river to different degrees. The dilution factor necessary to achieve no more than 50% mortality in the Thamnotox test (Ldf(50)) varied from >300 at the most acidic site, to 7 for water of pH 2.6 and 1.5 for water of pH 4.5. Toxicity was best explained from both low pH and high concentrations of metals, especially Al and Fe. The key role of Al and Fe in the toxicity was confirmed by relating concentrations of the different compounds in the river water to toxicity data from the literature. EDTA addition did not significantly influence Ldf(50) or the lethal pH 50% (LpH(50)), suggesting a large effect, besides cationic components and pH, of anions (F, SO(4) and Cl).     

Atmospheric versus lithogenic contribution to the composition of first- and second-order stream waters in Seoul and its vicinity

The spatial variations in the chemistry of first- and second-order stream waters (N = 65) were investigated in the easterly bound of Seoul in order to assess the effects of urban air pollution on surface water chemistry. The sulfate (SO4(2-)) was high (range 3.9-17.8 mg l(-1), mean 11.8 mg l(-1)) within 30 km away from the center of Seoul, compared to the levels (range 1.1-7.7 mg l(-1), mean 4.3 mg l(-1)) observed in remote areas (30-70 km away). Both graphical examination and statistical evaluation (variogram) of sulfate concentration data consistently showed the decrease of sulfate concentration with increasing distance. The results of mass balance modeling also indicate that the concentrations of SO4(2-), Cl- and Na+ may be affected mainly by dry/wet deposition. However, the spatial variations of major cations such as Ca2+ and Na+ are well explained by the reaction of rainwater with diverse rocks in the watercourse. The water type was found to change from Ca(-Na)-SO4) type to Ca(-a)-HCO3 type with the increasing distance. It is thus inferred that the pollutants like SO2 emitted from strong man-made source areas of Seoul are transported to the considerable distance (at least 30 km away) by westerlies and that such mechanism may lead to the changes of the anion composition in surface water. In the remote area (> 30 km away from Seoul), the stream water chemistry appears to be influenced more effectively by the weathering of rock-forming minerals.     

Characterization of natural organic matter from eight Norwegian surface waters: The effect of ash on molecular size distributions and CHN content

Natural organic matter (NOM) was isolated by reverse osmosis (RO) from eight surface waters in southern Norway. The freeze-dried samples were reconstituted in deionized water and part of the sample was dialysed against HCl. Samples of both the dialysed and non-dialysed materials were then ultrafiltered to give fractions: >50 000 dal., <50 000 but >10 000 dal. and <10 000 dal. nominal molecular weights (NMW). Dialysis against acid reduced the ash content of the samples by 68±14%. Non-dialysed NOM has a preponderance of carbon in the largest fraction (52.7±30%), while after dialysis, the smallest fraction of NOM has the greatest carbon content (52.2±9.7%). In addition to altering the overall apparent size distributions of the NOM fractions, dialysis generally reduces the amount of nitrogen relative to carbon in the NOM samples. The latter observation appears to be the result of losses of small molecular size organic matter that is enriched in nitrogen.     

Naturally occurring thallium: a hidden geoenvironmental health hazard?

This paper illustrates a real environmental concern and draws attention to the fact that natural processes can mobilize thallium (Tl), a highly toxic metal, which may enter the food chain as a "hidden health killer" with severe health impacts on local human population. Natural processes may be exacerbated by human activities such as mining and farming, and may cause enrichment of Tl in the environment. In geochemically anomalous areas with concentrated levels of Tl in the surface environment (bedrocks, waters, soils, and crops), such as the Lanmuchang area in southwestern Guizhou Province, China, it is essential to establish base-level values and to pay heed to the geological context of "natural contamination," as high concentrations of Tl in bedrocks/ores (6-35,000 mg/kg) can lead to enrichment of Tl in the aquatic system (0.005-1100 microg/l in groundwaters and 0.07-31 microg/l in surface waters) and soil layers (1.5-124 mg/kg). In sensitive areas such as the Yanshang area of southwestern Guizhou, elevated natural levels of Tl from bedrocks may also cause higher concentrations of Tl in the surface environment, and thus more attention must be paid to geoenvironmental management of human activities if socio-economic catastrophes are to be avoided. Due to high uptake of Tl by crops, Tl can be transferred from soils to crops and remarkably concentrated in food crops. Concentrations of 1-500 mg/kg Tl based on dry weight (DW) were determined in many food crops growing on Tl-contaminated arable soils from the Lanmuchang area. The daily intake of 1.9 mg of Tl from consumed food crops was estimated for the local adult inhabitant of Lanmuchang. Thus, Tl is regarded as a latent health hazard with potential risk of toxicity in humans within areas of "natural" contamination by Tl.