Long-term nitrate increases in two oligotrophic lakes, due to the leaching of atmospherically-deposited N from moorland ranker soils

During the last 50 years nitrate concentrations in Buttermere and Wastwater (Cumbria, UK) have risen significantly, by 70 and 100%, respectively. By estimating contemporary nitrate fluxes in the lakes' catchments and in sub-catchments and comparing them with the fractional areas of different soil types, it is deduced that the surface water nitrate is derived almost entirely from organic-rich ranker soils that have a limited ability to retain atmospherically-deposited nitrogen. Little or no nitrate leaches from the other major soil type, a brown podzol, despite it having a lower C:N ratio (12.0 g g(-1)) than the ranker (17.0 g g(-1)), nor is there much contribution from the small areas of improved (chemically fertilised) grassland within the catchments. Although some nitrate leaching is occurring, total N losses are appreciably smaller than atmospheric inputs, so the catchment soils are currently accumulating between 3 and 4 g N m(-2) a(-1).     

Historical mercury contamination in sediments and catchment soils of Diss Mere, UK

A 5.3 m sediment core and soil samples were taken from Diss Mere and its catchment. The sediment core was dated and Hg analysed on the sediment and soil samples. The Hg record of the sediment core shows that Diss Mere has been contaminated for the past thousand years and the historical trends in sediment contamination are in good agreement with the development of the weaving industry in Diss and hemp cultivation in the region. Mercury contamination in Diss Mere has been significant and reached a peak in the mid-19th century with sediment Hg concentrations over 50 μg g⁻¹. Elevated Hg concentrations were also found in contemporary soils in residential areas with former industrial land use. Although local hemp cultivation and the traditional weaving industry were abandoned a hundred years ago, Hg contamination caused by these activities still exists in the catchment, and affects the lake.     

Use of the modified BCR three-step sequential extraction procedure for the study of trace element dynamics in contaminated soils

The modified BCR three-step sequential extraction procedure was used to examine the temporal dynamics of trace elements in soils contaminated by an accidental spill from an opencast mine in south-west Spain. Soils were mainly contaminated with pyritic sludge and acidic wastewater, whereas some soils were affected only by acidic wastewater. The distributions obtained for both some major (Ca, Fe and Mn) and trace elements (As, Cd, Cu, Pb and Zn) in the sludge and soil samples taken at different times after the accident, 1-3 months and 21 months, were compared. Sequential extractions were useful in identifying different sources of contamination, and in obtaining additional information on the solubility of secondary minerals formed by pyrite oxidation. Thus, the effectiveness of the BCR procedure has proved to be a useful tool for predicting short- and long-term mobility of trace elements, even in complex environmental scenarios.     

Accumulation of mercury and methylmercury by mushrooms and earthworms from forest soils

Accumulation of total and methyl-Hg by mushrooms and earthworms was studied in thirty-four natural forest soils strongly varying in soil physico-chemical characteristics. Tissue Hg concentrations of both receptors did hardly correlate with Hg concentrations in soil. Both total and methyl-Hg concentrations in tissues were species-specific and dependent on the ecological groups of receptor. Methyl-Hg was low accounting for less than 5 and 8% of total Hg in tissues of mushrooms and earthworms, respectively, but with four times higher concentrations in earthworms than mushrooms. Total Hg concentrations in mushrooms averaged 0.96 mg Hg kg⁻¹ dw whereas litter decomposing mushrooms showed highest total Hg and methyl-Hg concentrations. Earthworms contained similar Hg concentrations (1.04 mg Hg kg⁻¹ dw) whereas endogeic earthworms accumulated highest amounts of Hg and methyl-Hg.     

Sorption of mercury (II) in Amazon soils from column studies

The sorption of Hg (II) onto four different types of Amazon soils from the A-horizon was investigated by means of column experiments under saturation conditions and controlled metal load. Higher organic matter contents in the soil resulted in higher Hg (II) adsorptions, reaching values as high as 3.8 mg Hg g⁻¹ soil. The amount of mercury adsorbed on a soil column (Q) shows a very poor correlation with soil clay content (r² = 0.2527), indicating that Hg sorption in these topsoil samples is chiefly governed by the organic matter content. Desorption experiments using Negro River (Amazon) waters were conducted using soil saturated with Hg (II) in order to better understand the metal leaching mechanism. The amount of Hg (II) released from soils was around 30% of the total sorbed mercury upon saturation, suggesting that mercury sorption in the soils present in the catchment area of the Negro River basin is not a reversible process.     

Potential application of a semi-quantitative method for mercury determination in soils, sediments and gold mining residues

An alternative, low cost method for analyzing mercury in soil, sediment and gold mining residues was developed, optimized and applied to 30 real samples. It is semiquantitative, performed using an acid extraction pretreatment step, followed by mercury reduction and collection in a detecting paper containing cuprous iodide. A complex is formed with characteristic color whose intensity is proportional to mercury concentration in the original sample. The results are reported as range of concentration and the minimum detectable is 100 ng/g. Method quality assurance was performed by comparing results obtained using the alternative method and the Cold Vapor Atomic Absorption Spectrometry techniques. The average results from duplicate analysis by CVAAS were 100% coincident with alternative method results. The method is applicable for screening tests and can be used in regions where a preliminary diagnosis is necessary, at programs of environmental surveillance or by scientists interested in investigating mercury geochemistry.     

Long-term trends in mercury and PCB congener concentrations in gannet (Morus bassanus) eggs in Britain

Gannet (Morus bassanus) eggs from Bass Rock (North Sea) and Ailsa Craig (eastern Atlantic) were monitored for PCB congeners (1990-2004) and total mercury (1974-2004). Congener profiles for both colonies were dominated by PCBs 153, 138, 180, 118 and 170. All declined in concentration at Ailsa Craig but some (153, 170, 180) remained stable or increased slightly at Bass Rock. Egg congener concentrations at Bass Rock were typically 10-fold higher than at Ailsa Craig by 2002, and Principal Component Analysis indicated that colony differences were driven by the dominant congeners. Egg mercury concentrations were significantly lower at Bass Rock than at Ailsa Craig and temporal trends differed, there being a significant decline at Ailsa Craig but a marginal increase at Bass Rock. Our results suggest there may be differences in contamination between the eastern Atlantic and North Sea and/or there are colony differences in prey selection and associated contaminant loads.     

Blood dynamics of mercury and selenium in northern elephant seals during the lactation period

The effects of reproduction and maternal investment (i.e., milk transfer) on trace element levels remain poorly understood in marine mammals. We examined the blood dynamics of mercury (Hg) and selenium (Se) during lactation in the northern elephant seal (Mirounga angustirostris), a top predator from the North Pacific Ocean. Total Hg and Se levels were measured in whole blood and milk of 10 mother-pup pairs on days 5 and 22 of lactation. Both Hg and Se were transferred to offspring through the milk. Results suggested that the maternal transfer of Se was prominent during lactation, whereas the Hg transfer was larger during gestation. The lactation period affected Hg and Se levels in the blood of elephant seal mothers and pups. Physiological processes and their relationship to body condition should be considered carefully when interpreting trace element levels in the framework of biomonitoring.     

Determinants of exposure to mercury in hair from inhabitants of the largest mercury mine in the world

Mercury exposure of the local population was assessed in two areas of the Almadén mercury mining district, Spain, which has been the world’s largest producer of this element. Two groups, who are exposed to different sources of mercury, from a point source in Almadén and a diffuse source hundreds of kilometres away in the same region, were studied. Total mercury (THg) in human hair ranged from 0.20 to 9.35 mg kg⁻¹ and the mean value was 2.64 mg kg⁻¹. About 87% of subjects had THg levels in excess of the EPA reference dose (RfD = 1.0 mg kg⁻¹), while a high percentage (68%) of them live in Almadén. There was a clear increase in hair Hg with reported fish consumption and the highest mean hair mercury level was 4 times the RfD in a group who had reported the highest consumption of fish. For the whole group, there was a significant effect of age, gender and fish consumption in relation to Hg concentration in the hair. Nevertheless, when both groups were tested separately by means of a multivariate regression model, there was significant exposure in those living near the mine area. Several factors such as age, gender and fish consumption remained statistically significant and were associated with THg. The main conclusion is that people living close to the hot spot are more impacted by mercury than people living further away. The intake of Hg through consumption of fish is an important parameter for Hg exposure; however, in the case of people living close to the hot spot, their levels are related to the highly Hg-impacted living environment.     

基于王水石墨密封消解体系-原子荧光法测定土壤和沉积物中汞、砷

为解决土壤和沉积物样品中的汞、砷前处理中的一些问题,如耗时长、清洗流程复杂及汞污染等,建立了一种基于王水石墨密封消解体系的前处理新方法,结合原子荧光可用于土壤和沉积物中Hg和As的测定。在最优条件下,2种重金属元素测定结果表明,本方法具有较低的相对误差 (Hg, -9.3%~9.3%; As,-7.0%~5.1%) ,较高的加标回收率 (Hg, 93.2%~104.5%; As, 95.9%~103.5%) 。此外,本方法相关性能指标均优于现行标准方法,具有稳定性好、精密度好、准确度高等优点。更重要的是,本方法因采用成本低廉的一次性塑料管,无需消解管清洗,避免了汞的污染。而且,消解过程无需其它操作,消解液用量少,具有操作简单、成本低、无汞污染等优点,可用于大通量土壤和沉积物Hg、As含量的测定。     

Gaseous mercury emissions from unsterilized and sterilized soils: The effect of temperature and UV radiation

Mercury (Hg) emissions from the soils taken from two different sites (deciduous and coniferous forests) in the Adirondacks were measured in outdoor and laboratory experiments. Some of the soil samples were irradiated to eliminate biological activity. The result from the outdoor measurements with different soils suggests the Hg emission from the soils is partly limited by fallen leaves covering the soils which helps maintain relatively high soil moisture and limits the amount of heat and solar radiation reaching the soil surface. In laboratory experiments exposure to UV-A (365 nm) had no significant effect on the Hg emissions while the Hg emissions increased dramatically during exposure to UV-B (302 nm) light suggesting UV-B directly reduced soil-associated Hg. Overall these results indicate that for these soils biotic processes have a relatively constant and smaller influence on the Hg emission from the soil than the more variable abiotic processes.     

Effect of biochar amendment on sorption and leaching of nitrate, ammonium, and phosphate in a sandy soil

When applied to soils, it is unclear whether and how biochar can affect soil nutrients. This has implications both to the availability of nutrients to plants or microbes, as well as to the question of whether biochar soil amendment may enhance or reduce the leaching of nutrients. In this work, a range of laboratory experiments were conducted to determine the effect of biochar amendment on sorption and leaching of nitrate, ammonium, and phosphate in a sandy soil. A total of thirteen biochars were tested in laboratory sorption experiments and most of them showed little/no ability to sorb nitrate or phosphate. However, nine biochars could remove ammonium from aqueous solution. Biochars made from Brazilian pepperwood and peanut hull at 600 °C (PH600 and BP600, respectively) were used in a column leaching experiment to assess their ability to hold nutrients in a sandy soil. The BP600 biochar effectively reduced the total amount of nitrate, ammonium, and phosphate in the leachates by 34.0%, 34.7%, and 20.6%, respectively, relative to the soil alone. The PH600 biochar also reduced the leaching of nitrate and ammonium by 34% and 14%, respectively, but caused additional phosphate release from the soil columns. These results indicate that the effect of biochar on the leaching of agricultural nutrients in soils is not uniform and varies by biochar and nutrient type. Therefore, the nutrient sorption characteristics of a biochar should be studied prior to its use in a particular soil amendment project.     

Relationship between the loading rate of inorganic mercury to aquatic ecosystems and dissolved gaseous mercury production and evasion

The purpose of our study was to test the hypothesis that dissolved gaseous mercury (DGM) production and evasion is directly proportional to the loading rate of inorganic mercury [Hg(II)] to aquatic ecosystems. We simulated different rates of atmospheric mercury deposition in 10-m diameter mesocosms in a boreal lake by adding multiple additions of Hg(II) enriched with a stable mercury isotope (²⁰²Hg). We measured DGM concentrations in surface waters and estimated evasion rates using the thin-film gas exchange model and mass transfer coefficients derived from sulfur hexafluoride (SF₆) additions. The additions of Hg(II) stimulated DGM production, indicating that newly added Hg(II) was highly reactive. Concentrations of DGM derived from the experimental Hg(II) additions (“spike DGM”) were directly proportional to the rate of Hg(II) loading to the mesocosms. Spike DGM concentrations averaged 0.15, 0.48 and 0.94 ng l⁻¹ in mesocosms loaded at 7.1, 14.2, and 35.5 μg Hg m⁻² yr⁻¹, respectively. The evasion rates of spike DGM from these mesocosms averaged 4.2, 17.2, and 22.3 ng m⁻² h⁻¹, respectively. The percentage of Hg(II) added to the mesocosms that was lost to the atmosphere was substantial (33–59% over 8 weeks) and was unrelated to the rate of Hg(II) loading. We conclude that changes in atmospheric mercury deposition to aquatic ecosystems will not change the relative proportion of mercury recycled to the atmosphere.     

Periphyton as a bioindicator of mercury pollution in a temperate torrential river ecosystem

Mercury presents a potential risk to the environment and humans, especially in its methylated form. It is among the highest priority environmental pollutants. River Idrijca (Slovenia) is highly contaminated with mercury due to past mercury mining. The aim of this work was to investigate whether the periphyton community in rivers such as Idrijca is a suitable indicator of Hg pollution and of changes in mercury methylation and could serve as an early warning system of increased input of MeHg in the food chain. Periphyton is the only site of primary production in temperate torrential rivers such as Idrijca and is therefore an important link in the food chain. It is also a potential site of Hg accumulation and its introduction to higher trophic levels. Our aim was to assess the response of the periphyton to seasonal and spatial variations in mercury levels and to evaluate its potential as an early warning system of changes in mercury reactivity and mobilization The results indicate that periphyton in a torrential river is too complex and unpredictable to be used as a sole indicator of mercury concentrations and changes in the river. Nevertheless, it can complement environmental measurements due to its importance in the riverine food web.     

Characteristics of mercury speciation in Minnesota rivers and streams

Patterns of mercury (Hg) speciation were examined in four Minnesota streams ranging from the main-stem Mississippi River to small tributaries in the basin. Filtered phase concentrations of methylmercury (MeHg), inorganic Hg (IHg), and dissolved organic carbon (DOC) were higher in all streams during a major summertime runoff event, and DOC was enriched with MeHg but not with IHg. Particulate-phase MeHg and IHg concentrations generally increased with total suspended solids (TSS) concentrations but the event data did not diverge greatly from the non-event data, suggesting that sources of suspended sediments in these streams did not vary significantly between event and non-event samplings. The dissolved fractions (filtered concentration/unfiltered concentration) of both MeHg and IHg increased with increasing DOC concentrations, but varied inversely with TSS concentrations. While MeHg typically constitutes only a minor portion of the total Hg (THg) in these streams, this contribution is not constant and can vary greatly over time in response to watershed inputs.     

Macro-porosity and leaching of atrazine in tilled and orchard loamy soils

Atrazine is the most commonly detected herbicide in the groundwater. Leaching of atrazine largely depends on soil management practices. The aim of this study was to examine leaching of atrazine in tilled and orchard silty loam soils. The experimental objects included: conventionally tilled field (CT) with main tillage operations including pre-plow (10 cm) + harrowing, mouldboard ploughing (20 cm), and a 35 year-old apple orchard (OR) with a permanent sward. To determine leaching of atrazine soil columns of undisturbed structure were taken with steel cylinders of 21.5 cm diameter and 20 cm high from the depth of 0–20 cm. All columns were equilibrated at water content corresponding to field capacity (0.21 kg kg⁻¹). Atrazine suspended in distilled water was dripped uniformly onto the surface of each column. Then water was infiltrated and breakthrough times of leachates were recorded. Atrazine concentration in the leachates was determined by means of HPLC Waters. Macro-porosity and percolation rate were higher in OR than CT soil. Cumulative recovery % of the atrazine applied was 1.267% for OR and approximately one third more from the CT soil but the rate of leaching (per unit of time) was greater from the OR soil. The lower leaching under OR than CT can be due to a greater SOM and the presence of earthworm burrows with organic burrow linings that could adsorb atrazine and contribute to preferential flow allowing solutes to bypass parts whereas the greater rate of leaching due to a greater infiltration rate.The results indicate potential of management practices for minimizing atrazine leaching.     

Distribution of polycyclic aromatic hydrocarbons in agricultural soils in South Korea

The content and type of polycyclic aromatic hydrocarbons (PAH) in soils from paddy fields and upland areas in South Korea were determined using gas chromatography linked to mass spectrometry (GC–MS). The distribution map of total PAH content was obtained as a contour plot using a geographical information system. The overall distribution of PAH was found to be closely related to the pollution sources, the size of city and the type of industry. The average content of total PAH in all samples was 236 μg kg⁻¹, and the range was from 23.3 to 2834 μg kg⁻¹. The highest concentrations were found in soils sampled near iron processing plants. The concentration of PAH decreased in the order fluoroanthene>benzo(b)fluoroanthene>pyrene. Special PAH compound ratios, such as phenanthrene/anthracene and fluoroanthene/pyrene, were calculated to evaluate the origin. The collected data suggested that the pyrogenic origins such as motor vehicle exhaust and heavy industry emission were the dominant source of PAH in Korean soils.     

Sequestration of organochlorine pesticides in soils of distinct organic carbon content

In the present study, five soil samples with organic carbon contents ranging from 0.23% to 7.1% and aged with technical dichlorodiphenyltrichloroethane (DDT) and hexachlorocyclohexane (HCH) for 15 months were incubated in a sealed chamber to investigate the dynamic changes of the OCP residues. The residues in the soils decreased over the incubation period and finally reached a plateau. Regression analysis showed that degradable fractions of OCPs were negatively correlated with soil organic carbon (SOC) except for α-HCH, while no correlation was found between degradation rate and SOC, which demonstrated that SOC content determines the OCP sequestration fraction in soil. Analysis of the ratio of DDT and its primary metabolites showed that, since it depends on differential sequestration among them, magnitude of (p,p′-DDE + p,p′-DDD)/p,p′-DDT is not a reliable criterion for the identification of new DDT sources.     

Relation of enhanced Pb solubility to Fe partitioning in soils

It is well documented that Pb solubility may be related to Fe chemistry in soils and enhanced Pb solubility may occur under certain reducing conditions; however, quantification of such relationships is unavailable. Based on metal classification, Pb (II) and Fe (II) are similar in some chemical characteristics. Thus, competition between Pb and Fe for ligands in soils may be important in determining Pb solubility. In this paper, Pb solubility was examined in a sandy soil after spiking with Pb and incubating for 40 days under water-flooded or non-water-flooded conditions. Solution chemistry in soil columns was adjusted using different concentrations of NaCl, CaCl(2) and deionized water of varying pH before incubation. The results showed that Pb solubility in the soil was not correlated well with pH, dissolved organic C or aqueous Fe concentrations. However, an index of Fe partition behavior using the ratio of aqueous Fe to sorbed Fe was related to Pb solubility. Enhanced Pb solubility occurred only when the index was < approximately 2 kg l(-1). The index can be a simple measure of Fe's ability to compete with Pb for ligands in solution. The ability of Fe to compete with Pb decreases as the index decreases and as the ratio approached its minimum, substantial increases in Pb solubility will be expected. In general, the index was not sensitive to changes in solution chemistry. A similar trend was observed using one data set published in the literature.     

Immobilization of mercury by pyrite (FeS2)

Elemental mercury (Hg⁰) is a metal with a number of atypical properties, which has resulted in its use in myriad anthropogenic processes. However, these same properties have also led to severe local subsurface contamination at many places where it has been used. As such, we studied the influence of various parameters on Hg(II) sorption onto pyrite (pH, time, Hg(II) concentration), a potential subsurface reactive barrier. Batch sorption studies revealed that total Hg(II) removal increases with both pH and time. X-ray absorption spectroscopy analysis showed that a transformation in the coordination environment at low pH occurred during aging over 2 weeks, to form an ordered monolayer of monodentate Hg-Cl complexes on pyrite. In column studies packed with pure quartz sand, the transport of Hg(II) was significantly retarded by the presence of a thin pyrite-sand reactive barrier, although dissolved oxygen inhibited Hg(II) sorption onto pyrite in the column.