The effect of alkaline dust decline on the precipitation chemistry in northern Japan

The precipitation chemistry in northern Japan, especially Hokkaido, has been investigated since 1982. This area has often been found to have high concentrations of alkaline road dust (asphalt dust) in the air, caused by the use of studded tires during the winter. It is well known that the composition of precipitation in these areas is often dominated by asphalt dust including calcium bicarbonate. However, recently the concentration of asphalt dust in the air has decreased owing to a ban on the use of studded tires. Simultaneously, in precipitation, the lowering of pH values and the increase of hydrogen ion depositions have been occurring owing to the decrease of non-sea-salt calcium ions (nss-Ca²⁺) concentrations and depositions derived from asphalt dust. In addition, we found that a decrease of nss-Ca²⁺ firstly leads to a decrease of bicarbonate ions (HCO₃ ^?), the counter ion to nss-Ca²⁺ in asphalt dust. Therefore, the increase of H⁺ concentrations and depositions was great in comparison with the decrease of nss-Ca²⁺ concentrations and depositions in areas where the HCO₃ ^?concentrations, varied by pH, and depositions had been low. Furthermore, this variation was mainly observed in the ionic composition of snow cover and snowfall at sites along the Japan Sea in northern Japan during winter. In this area, the Acid Shock effect may become a serious problem from the decline of pH values in melting snow. Moreover, we found that ammonium ions and non-sea-salt sulfate ions depositions have also been decreasing in response to a decrease of nss-Ca²⁺ depositions, derived from asphalt dust. It seems that this phenomenon is caused by the decrease of asphalt dust concentrations in the air.     

An analysis of wet deposition of sulfate using a trajectory model for East Asia

A long-range transport model for East Asia was developed to estimate the wet deposition of sulfate. The model is a trajectory type which is appropriate for long-term analysis. Trajectories of air masses are calculated by tracing the wind field which changes spatially and temporally. The processes of reactions, rainout removal, intake of sulfate in cloud water into rain water, and dry and wet depositions are considered. It is possible to calculate the concentration of sulfate in precipitation at a receptor by performing material balance in a grid box containing the receptor.The results obtained by the long-range transport model were evaluated through comparison with observation data of acidic deposition. The observation was conducted at 21 stations throughout Japan for one year. The calculated amount of wet deposition of sulfate in Japan was 0.22Tg/y in S equivalent, while the observed amount was 0.29Tg/y. The long-range transport model can predict almost 80% of observed wet deposition. The contributions of domestic anthropogenic sources and volcanic eruption to wet deposition of sulfate in Japan were estimated using the longrange transport model. The ratio of the deposition of sulfate due to Japanese anthropogenic sources to that due to the Asian continental sources was about 1 to 2. Since air stream from the direction of the Asian continent dominates during winter, the contribution of Japan to wet deposition in the region which faces the Sea of Japan amounted to less than 15%. The contribution of the sulfur oxides from volcanoes was about 20%.     

近代黄河三角洲段渤海海岸线缓冲带土地利用时空特征分析

通过解译1986、1996和2001年遥感图像，获得了黄河三角洲海岸带土地覆被数据。将该地区土地覆被分为9种类型：水域、芦苇、林地、耕地、柽柳、柽柳芦苇、翅碱蓬獐茅、滩涂、建设用地，并将3 km宽的海岸带分为6个缓冲带，每个带宽0.5 km。运用ARC/INFO软件和景观生态学方法，研究了渤海海岸线缓冲带的土地利用和景观格局变化。主要结果如下：在空间上，1986年和2001年各缓冲带土地利用程度综合指数随着距海岸线距离的增大而升高，两者呈直线关系；但在1996年，两者之间未呈现直线关系。在时间上，各缓冲带土地利用程度综合指数逐年增加；除了优势度外，所研究的其他景观格局指标与距海岸线的距离没有显著关系。     

Ionic balance in the interaction of meadow-chestnut soils with saline groundwater under model experimental conditions

The effect of ascending migration of medium and highly saline sodium-sulfate groundwaters on the salinization of nonsaline meadow-chestnut soils was simulated and quantified in model column experiments over 10 months. Sodium from saline water accumulated in the soil as similar amounts of water-soluble and exchangeable compounds in lower soil horizons. Calcium accumulation as CaCl@2 in the topsoil and as gypsum throughout the profile was accompanied by substitution of Na for exchangeable Ca. Magnesium and chlorine mainly accumulated as soluble salts in the topsoil, and sulfate ions accumulated as gypsum through the profile and as soluble salts in the lower part of the column.     

Regional Characteristics of Cooper Corrosion Components in East Asia

Copper plates were exposed under shelters at 13 sampling sites in East Asia and their corrosion was analyzed. The corrosion products were first dissolved in water and then oxalic acid. Sulfate, nitrate and chloride in the solutions were measured by ion chromatography. The amounts of the three anions significantly differed depending on the atmospheric environment at the sites. Sulfate was a major part of the anions at Chongqing and Shanghai in China. Especially, at the urban sites in Japan, nitrate remarkably changed with the seasons, and often became the large anionic component in the summer. The amounts of chloride at most sites were at higher concentration levels compared with those at the rural sites in Japan. The anions in the copper corrosion must mainly reflect the impact of acid deposition.     

Characterization of Desulfovibrio sp. isolated from some lowland paddy field soils of Burkina Faso

In a wetland ecosystem such as lowland ricefields, the anaerobic mineralization of organic matter is a key mechanism for nutrient recycling (Jørgensen 1982; Freney et al. 1982). In the process which involves several bacterial groups, sulfate reducers (Watanabe and Furusaka 1980; Widdel 1988; Ouattara and Jacq 1992; Nozoe 1997), methanogens (Asakawa and Hayano 1995; Dianou et al. 1997), sulfur and ferric ion reducers (Jacq et al. 1991) become active when the soil becomes anoxic (Amstrong 1969). Sulfate reducers are common in flooded soils (Watanabe and Furusaka 1980; Widdel 1988; Furusaka et al. 1991). Reported densities in rice soils ranged from 10³ to 10⁵ g^-1 dry soils in Asia (Watanabe and Furusaka 1980) and from 10² to 10⁹ g^-1 dry soil in Sénégal (Ouattara and Jacq 1992). Among the sulfate reducers, the “classical” Desulfovibrio species are known to oxidize typical fermentation products such as hydrogen, lactate, pyruvate, and dicarboxylic acids (Widdel 1988). So far, data on the isolation and characterization of sulfate-reducing bacterial (SRB) strains from African rice paddy field soils study have been very limited.     

模拟土遗址中可溶盐运移规律的初步探索

采用常规的定性和定量分析方法,测定了陕西师范大学土遗址模拟坑中不同位置土壤含水率、可溶盐成分及含量。结果表明,这些可溶盐主要为钙和钠的硫酸盐类,它们随着水分沿竖直方向和水平方向不断地向遗址表面运移,最后在土壤表层积累堆积;利用X射线衍射仪(XRD)、环境扫描电子显微镜(SEM)和超景深三维立体显微镜(3DSDDM),分析了可溶性盐分对遗址土壤结构的破坏作用,结果表明,由于可溶性盐分在遗址表面的累积,可溶性盐分在遗址孔隙中形成了巨大内应力,使土壤颗粒之间的黏结力减小,土壤颗粒之间的距离拉大,使土体表面泛白酥解,严重时引起土颗粒的脱落和酥解。本研究为土遗址保护中盐害治理提供了依据,对保护大批濒临破坏的土遗址,推动文物保护的理论研究与实际工作均有重大意义。     

唐皇城含光门土遗址盐分病害分析与研究

唐皇城含光门土遗址中微溶-可溶盐导致地泛白、酥粉、片状脱落等病害极为严重。通过对土壤含水率、酸碱度(pH)、电导率测定以及微溶-可溶盐的X射线粉末衍射(XRD)、能谱(EDX)、扫描电子显微镜(SEM)分析,结果表明:唐皇城含光门东展厅土遗址微溶-可溶盐主要以硫酸钙类和硫酸钠类为主;西展厅五期断面土遗址主要以硫酸钙类、碳酸钙类为主。不同部位含盐量与水分的运移密切相关,随着距离水平地面高度的增加,含水率的的降低,微溶-可溶盐的含量降低。通过扫描电子显微镜观察发现,硫酸钙类是导致土遗址酥粉、脱落病害的主要原因。     

Seasonal and Spatial Variations in the Chemical and Sulfur Isotopic Composition of Acid Deposition in Niigata Prefecture, Japan

The following measurements were carried out to clarify acid deposition in Niigata Prefecture, an area facing to the Sea of Japan. 1) Acid deposition fluxes and sulfur isotopic ratios of atmospheric deposition were measured at 9 sites in the prefecture in 1999. 2) Atmospheric deposition was collected daily at one site in 1997, to measure the sulfur isotopic variations of sulfate together with the air mass trajectory for each deposition. It became clear that: (a) The major component that acidifies atmospheric deposition is sulfuric acid. (b) Sulfate deposition increases in winter in the whole study area. (c) The sulfur isotopic ratios indicate that sulfur dioxide emitted from China affects the whole study area in winter. (d) Winter deposition of sulfate estimated to derive from coal combustion in China account for half of nss-sulfate deposition in average at 9 sites.     

Der Einfluß variierter Düngergaben von Stickstoff,Kupfer und Magnesium auf den Ertrag von Hafer

The Influence of varying Amounts of Nitrogen, Copper and Magnesium on the Yield of Oat 1. In pot experiments with oat high amounts of copper (500 mg) copper sulfate/pot, comparable to 50 kg (Cu/ha) together with a high nitrogen supply as calcium nitrate led to a remarkable increase in yield of grain in comparison to a normal copper fertilization (50 mg copper sulfate/pot, comparable to 5 kg Cu/ha). When using high amounts of ammonium sulfate the observed effect of high amounts of copper was only small. 2. According to the results and to the copper content and copper uptake of the plant it was concluded, that nitrogen fertilization given as ammonium sulfate increased the availability of soil copper and/or fertilizer copper presumably by affecting the soil reaction. Nitrogen fertilization given as calcium nitrate therefore needs a higher copper level in the root medium either from soil or fertilizers in order to obtain the maximum yield. 3. It was assumed that the form of nitrogen fertilizers was responsible for the different availability of copper in these experiments, as the amount of available copper in the soil increased with the lowering of soil pH due to ammonium sulfate addition. 4. The high copper supply to the soil remarkably reduced the harmful effect of high amounts of nitrogen given as calcium nitrate but not as ammonium sulfate. 5. The nitrogen fertilization with calcium nitrate, especially in combination with a high copper supply, resulted in the reducing effect of a magnesium deficiency. 6. The harmful effect of high amounts of nitrogen, especially in the ammonium sulfate form, upon yield was reduced by an optimal magnesium supply. 7. The results presented suggest that for evaluating the copper status of the soil and for estimating the demands of copper fertilization, soil reaction and its change by the form of nitrogen fertilizers should more be taken in consideration.     

Geochemical Characteristics of Acidic Stream Water on Yakushima Island,a World Natural Heritage Site

We determined the chemical compositions of acidic stream waters on the rural, mountainous island of Yakushima (YK), and compared them with those of near-neutral stream waters in other mountainous watersheds in Japan. The pH and concentrations of the predominant sea-salt components (i.e., Cl^?, Na⁺, Mg²⁺) in YK water, particularly in streams with small watersheds, decrease with elevation, while the concentration of Al increases. In contrast, water in northwestern YK contains higher concentrations of non-sea-salt SO₄^2? and NO₃^? and of rock-derived cations such as Si and Ca²⁺ than water in eastern to southern YK. This clearly shows that the anthropogenic pollutants on YK are dominantly derived from the northwestern to western Asian continent rather than from Japan's main islands, which lie to the northeast. These pollutants are responsible for stream acidification on YK and for accelerating chemical weathering, mainly of plagioclase, in northwestern YK. Large amounts of acid rain on YK may enhance the formation of secondary minerals that strongly adsorb heavy metals, which can partly account for the low concentrations of heavy metals in YK waters.     

Quantification of In Situ Denitrification Rates in Groundwater Below an Arable and a Grassland System

Growing season rain and cloud events were sampled between 1984–2010 at Lakes of the Clouds (LOC) (1,540 m above sea level (ASL)) which is 1.6 km SW of the summit of Mount Washington, NH (1,914 m ASL). Mount Washington's summit is in the clouds ca. 51 % of the time. All samples were measured for pH, while cations and anions were measured consistently from 1996 to 2010. Annual mean cloud and rain water hydrogen ion concentrations declined significantly from 1984–2010. Nighttime cloud and rain hydrogen, sulfate, ammonium, and nitrate ion concentrations were significantly greater compared to daytime. Ion mean concentrations declined over the 1996–2010 timeframe and more rapidly since 2005. Co-located filter-based aerosol measurement (PM_2.5) at LOC had higher ratios of ammonium to sulfate in summer daytime samples post (1995–2010) full implementation of the 1990 Clean Air Act Amendments. This suggests a shift towards more neutralized sulfate aerosol dissolution into clouds with relatively more ammonium and declines in acidity. The origin of cloud water sampled, which ranges from regional fronts to orographic lower elevation air mass uplift, along with the diurnally shifting nocturnal boundary layer that often puts the LOC site in and out of the mixed layer, likely contributes to the diurnal and inter-annual variability observed.     

Mercury Concentration and Monomethylmercury Production in Sediment: Effect of Dredged Sediment Reuse on Bioconcentration for Ragworms

The effect of dredged sediment reuse on the production and bioconcentration of monomethylmercury (MMHg) was investigated by examining sediments and ragworms found in dredge material banks and surrounding sites in the Venice Lagoon, Italy. Total Hg concentrations in the surface 20 cm of sediments were higher in the banks than in the surrounding sites, but MMHg concentrations were similar, which suggests reduced MMHg production in the banks. Monomethylmercury content in ragworms was significantly lower (p?<?0.05) in the banks than in the surrounding sites. In pore water, concentrations of both sulfate and Fe decreased with depth in the upper 20 cm of the dredge banks. In contrast, sulfate concentrations were constant with depth and large amounts of dissolved Fe occurred in the upper 20 cm of sediments of surrounding sites. Continuous sulfate reduction and possible precipitation of iron sulfide may decrease the production and bioconcentration of MMHg in the dredge material banks compared to the surrounding sites. Overall, the production of MMHg in sediments and its bioconcentration in benthic organisms were connected to the process of sediment diagenesis of organic matter through the control of pore water and sediment geochemistry involving iron and sulfur.     

Effect of acid deposition on forested catchment in the western Tokyo,Japan

Acid deposition and its effect on Andisols were investigated in the forest experimental station, the Rolling Land Laboratory (RLL), located in the Tama Hill region of Central Japan. The annual volume-weighted mean pH value of open bulk precipitation was 4.8 in the period 1990 to 1992. Nitrate deposition at RLL was larger than for sulfate, which was obviously different from results in Japan Environment Agency (JEA) stations or in study areas of Europe and North America. Abundant nitrate deposition was ascribed to the high emissions from a non-point source, mainly cars. Although sulfate concentration in throughfall fluctuated, its concentration in soil solution was kept at a low level. This was attributed to the high sulfate adsorption capacity of the Andisols.     

Seasonal and spatial studies on pesticide residues in surface waters of the Shinano river in Japan

Water samples collected once a week from early April 1996 to the end of August 1996 from four sites on the Shinano River in Japan were analyzed for pesticides and their metabolites using a gas chromatograph-mass spectrometer. Among the total of 53 chemicals found, 22 were herbicides, 15 were insecticides, 11 were fungicides, and 5 were metabolites. The concentrations of chemicals found ranged from 3 ng/L (bromobutide) to 8200 ng/L (isoprothiolane). Herbicides were found primarily during May and June at all four sites. Insecticides and fungicides were found primarily during July and August at all four sites. The presence of pesticides in the river water correlated with the time of pesticide application to the rice fields near the river.     

Diurnal Characteristics of Suspended Particulate Matter and PM<Subscript>2.5</Subscript> in the Urban and Suburban Atmosphere of the Kanto Plain,Japan

Suspended particulate matter (SPM) and PM_2.5 in the urban and suburban atmosphere of the Kanto Plain of Japan, which includes the Tokyo metropolitan area, during the period 22–26 July 2002 were characterized. Samples of SPM and PM_2.5 were collected by low-volume samplers at 6-h intervals at Suginami, Saitama, and Kisai. At all the sites, the major components of SPM and PM_2.5 were organic carbon (OC), elemental carbon (EC), and sulfate. The ion balance, the size distributions of the ionic species, and the high correlation between SO₄ ^2? and NH₄ ⁺ indicated that the main chemical form of sulfate was (NH₄)₂SO₄. The OC/EC ratios were larger in the daytime than in the nighttime. The correlation coefficients of OC, OC/EC, and SO₄ ^2? with ozone concentrations at inland sites (Saitama, Kisai) were higher than those at the coastal site (Suginami). Bound water and hydrogen and oxygen atoms associated with OC, the amounts of which were estimated with a mass closure model, contributed substantially to the total particle mass. The chemical characteristics of the particles indicated that two mechanisms led to high concentrations of SPM and PM_2.5: (i) an active photochemical process produced high concentrations of OC and sulfate, leading to a high concentration of (NH₄)₂SO₄ in the particles and to production of secondary organic aerosols; (ii) stable meteorological conditions resulted in accumulation of primary particles, mainly emitted from vehicle exhaust, resulting in high concentrations of OC and EC.     

Acid Toxicity Levels in Nova Scotian Rivers Have Not Declined in Synchrony with the Decline in Sulfate Levels

The Atlantic salmon (Salmo salar) resource of eastern Canada is impacted by acid rain in the Southern Upland (Atlantic Coast) area of Nova Scotia. Salmon runs in this area have become extinct in 14 rivers, are severely impacted in 20 rivers, and lightly impacted in 15 rivers. Water chemistry and fish communities in nine Southern Upland salmon rivers were studied from 1982 to 1996 as part of the effort to monitor the effects of the emission controlprograms in Canada and the United States. There hasbeen no statistically significant change in total ioncontent of Southern Upland river water, but there wasa significant decline in sulfate levels that was balanced by an increase in organic anions, and declines in calcium and magnesium that were balanced by increases in sodium and potassium. A geochemical scenario is proposed to account for these chemical changes. River water pH levels showed no overall linear trend, but at borderline toxicity sites the year-to-year variations in pH were correlated withchanges in juvenile salmon population densities. Tenfish species were collected, but none showed anysignificant overall time trend in population density.Fish species diversity was positively correlated with pH.     

Seasonal Sulfate Deposition and Export Patterns for a Small Appalachian Watershed

Sulfate deposition and exports from 1988–92 were analyzed for a small headwater catchment in north-central West Virginia. Annual sulfate inputs, estimated by applying throughfall-adjusted ratios to bulk deposition values, and outputs were approximately equal for the five years. Annual mean throughfall-adjusted deposition and export loads were 55.78 and 55.48 kg ha-1, respectively. While these results indicate the watershed has reached sulfate equilibrium relative to current deposition levels, seasonal sulfate accumulations and deficits were evident. Deposition and exports averaged 5.61 and 2.49 kg ha-1 mo-1, respectively, during the growing season, and 3.69 and 5.22 kg ha-1 mo-1 during the dormant season. Sulfur accumulated within the soil during the growing season because inputs of wet and dry sulfur deposition were high while outputs were negligible. The latter was due largely to the lack of runoff resulting from high evapotranspirational demands. By contrast, net sulfate losses occurred during dormant seasons, primarily due to high runoff, even though inputs declined during this season. Researchers working on other watersheds have interpreted similar input/output patterns to mean that sulfate accumulated during the growing season is the source of sulfate exported during the dormant season. However, radioisotopic evidence from a companion study on this watershed showed that some labeled sulfate applied to the watershed more than a year earlier was still present in the organic and mineral soil layers at the point of application (with some as soluble sulfate), and in soil water dispersed throughout the watershed. Its presence indicates that dormant season exports can originate from sulfate deposited over longer periods than just the previous growing season or even previous year. Volume-weighted concentrations in soil leachate suggest that dormant-season sulfate losses resulted from progressive depletion of the anion through the soil profile. During the fall and early winter, soluble sulfate was depleted in the upper soil horizons; in later winter, depletion occurred in the lower horizons.     

Relationships between afforestation,water chemistry and fish stocks in an upland catchment in south west Scotland

The soils and waters in the Galloway hills of south-west Scotland have undergone considerable acidification during the present century. The aims of this study were to examine the extent to which afforestation can influence water chemistry, and the occurrence of fish stocks within an individual catchment in this area. Studies were carried out at 45 sites in the Bladnoch catchment during 1994. River water samples were collected at all sites and determinations made of pH, total organic carbon, calcium and monomeric aluminium concentrations. In order to quantify the size and abundance of fish populations, electrofishing was carried out at 21 of the sites. Estimates of afforestation were made by a combination of field surveys and the use of 1∶:10 000 scale ordnance survey maps. The presence of coniferous trees had a substantial affect on water chemistry. In areas where the whole catchment was afforested, the water pH was 0.7 units lower than in unafforested areas (p<0.001). Afforestation was also correlated with low concentrations of calcium, and increases in the concentrations of monomeric aluminium and total organic carbon. There was a clear relationship between fish populations and water chemistry. Numbers of trout were positively correlated with pH (r ²=0.69; p<0.001), and with concentrations of calcium (r ²=0.55; p<0.001). The study has shown that salmonid fish populations are sensitive to acidity and the associated changes in river water chemistry; these problems were exacerbated by afforestation.     

Changes in Freshwater Acidification Trends in Canada's Atlantic Provinces: 1983–1997

Sixty-three lakes were sampled semi-annually for acid precipitation – related variables in Canada's Atlantic Provinces,Nova Scotia and Newfoundland from 1983 to 1997. A further 31 sites were sampled beginning in 1989 in Nova Scotia. We analyzedthe water chemistry data for trends in pH, acid neutralization capacity, sulfate and base cations using the whole data set for the original 63 sites and the most recent eight years' data for all sites. We also analyzed acid deposition at two CAPMoN precipitation chemistry sites located at the two extremes of thesampling region for trends. We found that hydrogen deposition decreased by 20% in Newfoundland and 30% in Nova Scotia, and sulfate decreased by 36 and 34%, respectively. Sulfate and basecations in lake waters showed decreases as expected, though lakeacidity and acid neutralization capacity did not show improvements. The conflicting trends in chemical variables suggest that though anthropogenically-induced weathering is diminishing in this region, conditions have not returned to `natural' background conditions.