Historical data of atmospheric sulfur in three monitoring periods for Europe

During the last 25 yr three major monitoring programs (EACN, OCED and EMEP) were conducted in Europe that furnished continental background air and precipitation quality data. Comparisons of these measured data show that SO₂ concentrations in air and sulfate ion concentrations in precipitation do not vary in parallel with changes in S emissions. This lack of correlation between emissions and ambient air and precipitation concentrations among the three networks is believed to be due mostly to differences in sampling and analytical procedures, as well as the shift in S emissions from low sources to high stacks.     

On the variability of simulated source-receptor relationships for sulfur deposition

The use of Lagrangian models to estimate source-receptor relationships for ambient SO₄ ⁼ concentrations and S deposition has become fairly widespread over the past several years. This paper addresses the sensitivity of long-term simulations of a Lagrangian S transport and deposition model to actual variations in SO₂ emissions and meteorological conditions. The variations of predicted source-receptor relationships due to (1) the inclusion of day to day variations in emissions strength as opposed to the use of the annual average daily emission rate and (2) year-to-year variations in meteorological conditions were studied to identify causes of uncertainty in a Lagrangian model. The results suggested that adding information on day to day emission variations for a specific point source resulted in variations in estimated S wet deposition of the order of only 20% within 500 km of the source.Year-to-year variations in meteorological conditions, on the other hand, resulted in variations in predicted S wet deposition of the order of 50% for some receptors. The variation in estimated source-receptor relationships for a given source/receptor combination was found to range as high as 70% over a 5-yr modeling period.     

Critical loads of sulfur and nitrogen for lakes II: Regional extent and variability in Finland

The concept of critical loads has been developed to assist in the design of environmentally sound abatement strategies for the emissions of acidifying compounds. In this paper the critical loads of S and N for lakes in Finland are computed and mapped, based on methods presented in an accompanying paper. The employed steady-state mass balance model allows the simultaneous evaluation of the reductions required of S and N deposition exceeding these critical loads. Special emphasis has been put on the presentation of the spatial variability and the uncertainty of the critical loads and their exceedances. The derived critical loads of S and N for lakes in Finland show a substantial spatial variability. The highest exceedance of critical loads is presently estimated in the south-east of the country, where up to 80% of the lakes show an exceedance of the critical loads of S. The evaluation of two emission scenarios shows that only “maximum feasible reductions” would be sufficient for protecting most Finnish lakes from the impacts of acidic deposition. The results of this study form a basis for setting national targets for emission reductions in Finland.     

The assessment of impacts of possible climate changes on the results of the IIASA rains sulfur deposition model in Europe

An analysis is made of the relationship between patterns in atmospheric circulation in Europe and the temperature regime of the Northern Hemisphere over the same period. The basis for classifying different types of atmospheric circulation or large-scale weather paterns [commonly known as Grosswettertypes (GWT-s) or Grosswetterlagen (GWL-n)] is the identification of the position of centers of cyclones, ridges and troughs. The linear regression between the frequency distribution of GWL-n and the deviation in the mean annual Northern Hemisphere extratropical temperatures from the 90-yr period (1891 to 1980) were tested. The results show that the null hypothesis, i.e. that there no linear relationship, is rejected at the 95% probability level (assuming a normal distribution) for several GWT-s and GWL-n. Changes in GWT-s and GWT-n frequency distribution associated with global warming could substantially change the long-range transport of pollutant over Europe. For example, the decrease in frequency of zonal circulation regimes and the more frequent meridional and blocked circulations (especially easterly flows) could result in a decrease of the existing net export of S pollutants from western to eastern Europe during the winter months.     

四川省土壤有效硫状况及硫肥效应研究

通过对四川省 6类 32 9个土壤样品的有效硫的分析 ,结果表明缺硫及潜在性缺硫土样占总样本的 2 3 1 % .但结合田间试验 ,在四川盆地特定环境条件下 ,即使土壤耕层有效硫处于缺乏范围 ,增施硫肥对玉米、小麦、油菜产量无明显增加 ,并就产生的原因作了初步分析 .通过对土壤硫素平衡的测算 ,预测在近期内 ,四川盆地主要农耕地不会发生大面积缺硫问题     

Polycyclic aromatic hydrocarbons in atmospheric particulate depositions and urban soils of Moscow,Russia

Purpose

The study was conducted to quantify the polycyclic aromatic hydrocarbons (PAHs) accumulation in urban soils from different functional areas via atmospheric inputs with particulate matter.

Materials and methods

PAH concentration and pattern were measured in the particulate matter of snow depositions, in the upper layers of artificial soils from densely built-up areas and in the undisturbed natural soils (Umbric Retisols) from green park area. Samples were collected in 2011–2013 at 58 sites with different traffic activities located at the territory of the Eastern Administrative Okrug of Moscow. The soil samples and filters with particulate matter were extracted by pressurized liquid extraction using Dionex ASE200. Clean-up analyses were performed on SPE cartridges filled with silica gel. Concentrations of PAHs were determined by high-performance liquid chromatography using an Agilent 1100 System equipped with fluorescent detector.

Results and discussion

Mean values of PAH input with snow particles were 45–57 μg/m² for recreational and residential zones, and 140–264 μg/m² for traffic zones. The samples of depositions from different functional areas showed a similar PAH pattern and consisted primarily of 3–4-ring PAHs. Total PAH concentrations in upper layers of artificial soils showed similar mean values of 1.43–2.21 μg/g for all functional zones. The PAH content in soils from the park area was twofold lower than that from the built-up area (0.34–0.63 μg/g), despite equal levels of atmosphere contamination on these territories. The upper layers of natural soils from recreational and traffic zones showed slight differences in PAH content, though PAH input with snow was fivefold higher in the traffic zone. Compared with airborne depositions, soils contained significant amounts of 5–6-ring PAHs.

Conclusions

A high level of soil PAH contamination in urban areas of Moscow, several orders of magnitude higher than the current PAH input to them from the atmosphere, indicates a lack of direct connection of the PAH pool in soils with this source. The high PAH content in the upper layer of constructed soils can be the result of repeated use of materials subjected to a constant technogenic impact for the production of artificial soils.

     

Determination of total sulfur in plant materials using an automated sulfur analyzer

Abstract

An automated sulfur analyzer (ASA), which has been developed for sulfur analysis of coal and coke was evaluated for determination of total sulfur in plant materials. Plant materials containing from 0.15% to 0.75% sulfur have been analyzed with precision and accuracy superior to other accepted methods which are more tedious and time‐consuming. The direct reading unit is capable of making approximately one sulfur determination every three minutes.     

Microbial activities in forest soils exposed to chronic depositions from a lignite power plant

Atmospheric emissions of fly ash and SO₂ from lignite-fired power plants strongly affect large forest areas in Germany. The impact of different deposition loads on the microbial biomass and enzyme activities was studied at three forest sites (Picea abies (L.) Karst.) along an emission gradient of 3, 6, and 15 km downwind of a coal-fired power plant (sites Ia, II, and III, respectively), representing high, moderate and low emission rates. An additional site (site Ib) at a distance of 3 km from the power plant was chosen to study the influence of forest type on microbial parameters in coniferous forest soils under fly ash and SO₂ emissions. Soil microbial biomass C and N, CO₂ evolved and activities of l-asparaginase, l-glutaminase, β -glucosidase, acid phosphatase and arylsulfatase (expressed on dry soil and organic C basis) were determined in the forest floor (L, Of and Oh horizon) and mineral top soil (0-10 cm). The emission-induced increases in ferromagnetic susceptibility, soil pH, concentrations of mobile (NH₄NO₃ extractable) Cd, Cr, and Ni, effective cation exchange capacity and base saturation in the humus layer along the 15 km long transect significantly (P<0.05) reflected the effect of past depositions of alkaline fly ash. Soil microbial and biochemical parameters were significantly (P<0.05) affected by chronic fly ash depositions. The effect of forest type (i.e. comparison of sites Ia and Ib) on the studied parameters was generally dominated by the deposition effect. Alkaline depositions significantly (P<0.05) decreased the microbial biomass C and N, microbial biomass C-to-N ratios and microbial biomass C-to-organic C ratios. Microbial respiration, metabolic quotient (qCO₂) and the activities of l-asparaginase, l-glutaminase, β-glucosidase, acid phosphatase and arylsulfatase were increased by long-term depositions from the power plants. Acid phosphatase had the highest specific (enzyme activities expressed per unit organic C) activity values among the enzymes studied and arylsulfatase the lowest. The responses of the microbial biomass and soil respiration data to different atmospheric deposition loads were mainly controlled by the content of organic C and cation exchange capacity, while those of enzyme activities were governed by the soil pH and concentrations of mobile heavy metals. We concluded that chronic fly ash depositions decrease litter decomposition by influencing specific microbial and enzymatic processes in forest soils.     

Temporal and spatial variability of total ozone content over Central Europe: analysis in respect to the biological effect on plants

The temporal and spatial variability of the total ozone content (TOC) is examined in respect to the biologically effective ultraviolet radiation on plants. TOC data from 1996 to 2000 over the domain of Central Europe were used. Variability is analysed using correlation and auto-correlation coefficients.The temporal auto-correlation analyses has shown that the only periodicity which could be found was a period of 1 year. The comparison between spatial correlation and the temporal auto-correlation delivers an equivalent value of zero for a distance between 400 and 500 km and at a time lag of 5 days. The influence of temporal and spatial variability of TOC on the biologically effective ultraviolet radiation was quantified by model calculations using action spectra of the DNA-damage and the generalised plant damage (GPD). These were undertaken for a certain location using TOC with various temporal delays or made at other locations with certain distances. The results show that the relative sensitiveness to spatial lags in TOC differs by a factor of three during the year with minimum in August and maximum around December. For temporal lags the sensitiveness changes by a factor of six between August and December.     

土壤中全硫测定——硫分析仪选择及方法优化

全硫含量是土壤调查项目中的必测项目。在燃烧法直接测定固体样品的硫分析仪中,高频红外碳硫仪检测限低,检测速度快,燃烧温度高,测定土壤标准物质的准确度高,是快速测定土壤中全硫的最佳仪器。应用高频红外碳硫仪测定样品过程中,坩埚空白、通氧流量、样品称样量、助熔剂添加量、定量方法等均会对测定结果准确度产生影响。通过对上述影响条件进行优化,研究确定了测定土壤中全硫含量的最佳条件:在严格控制坩埚空白的前提下,通氧流量设定为2～3L/min,依次称取0.1g样品(精度:0.0001g)、0.5g纯铁(精度:0.001g)和1.0g钨粒助熔剂(精度:0.001g)混合后上机分析,对不同浓度样品进行分段校正。值得注意的是,本研究证实了利用化学物质标准品建立工作曲线的可行性,为后期仪器优化和改进提供了宝贵思路。国家土壤标准物质测定结果的相对标准偏差(RSD)小于2%(n=6),测定值与标准值相对误差(RE)的绝对值小于1%(n=6),方法检出限为4.50 μg/g,说明方法的准确度和精密度高,适用于低含硫量土壤样品的批量检测。     

Characterization of sulfur retained by soils exposed to sulfur dioxide

Abstract

Soils have substantial capacity for sorption of sulfur dioxide (SO₂) but little is known about the nature of the sorbed S. Three surface soils varying in pH, organic matter, CaCO₃ equivalent and surface area were exposed to air containing 5% SO₂ and subsequently analyzed by ten different procedures to characterize the sorbed S. Most of the sulfur retained by soils after exposure to SO₂ could be recovered as CaCl₂‐extractable S, Ca(H₂PO₄)₂‐extractable S, or S released as H₂S by hydriodic acid (HI). Only small amounts of sulfur could be recovered as tetrachloromercurate (TCM)‐extractable S, S released as SO₂ by HCl, or S released as H₂S by HCl + Zn, HCl + Sn, or Raney Ni and NaOH. However, large amounts of S released as SO₂ by HCl were recovered from the air‐dry Webster and the moist Storden soils indicating that SO₂ sorption is influenced by organic matter in air‐dry soils and by CaCO₃ in moist soils.     

Effect of sulfur deficiency and excess on yield and sulfur accumulation in tomato plants

Abstract

Tomato (Lycopersicon esculentum Mill. var. hybrid 6C‐204) plants were grown for 95 days after germination until each one bore 6 ripe clusters in a greenhouse using nutrient solutions with nine added sulfate levels ranging from 0 to 105 me/1.

Sulfur‐deficiency symptoms and characteristics of plants growing under hign SO₄‐S levels were observed and described. Fruit yields were negatively affected by both S‐deficiency and high SO₄‐S concentrations. Top growth was affected more than root growth by changes in the amount of SO₄‐S supplied. The critical SO₄‐S concentration in the growth media ranged from 2 a 22.5 me/1.

Leaf sulfate‐S increased gradually in leaves and roots as SO₄‐S supply in the nutrient solution increased while organic‐S remained relatively constant. Leaf sulfate‐S critical value was growth stage dependent. Maximum yields at flowering were associated with leaf concentrations of 0.48–1.2% SO₄‐S and 0.25–0.35% organic‐S.     

Measurement of microbial sulfur in soil

A technique was developed to estimate the amount of sulfur held by the microbial population in soil. This method involves lysing the microbial cells with chloroform and measuring the S released to 10 mm CaCl₂ or 0.1 m NaHCO₃ extracts. Calculations of biomass-S were made from the experimentally determined proportion of cell S released. To determine this proportion, two species each of bacteria and fungi, which were grown at three concentrations of S, were added to the soil and treated with CHCl₃. The average values of 34.6% with CaCl₂ and 41.2% with NaHCO₃ were calculated for the proportion of microbial S extracted following CHCl₃ treatment. Biomass-S was found to represent approximately 2.3% of the total S in the soil.     

Effects of previous elemental sulfur applications on oxidation of additional applied elemental sulfur in soils

Oxidation of elemental sulfur (S⁰) in 20 Chinese agricultural soils was tested and the effects of previous S⁰ applications on the oxidation of additional applied S⁰ in selected soils were investigated using laboratory, greenhouse, and field experiments. Results showed that sulfur oxidative capacities presented great variability among 20 tested soils, with a coefficient of variation of 92.4%. There were no significant relationships between S⁰ oxidation and physical and chemical properties of the selected soil. Previous S⁰ amendment significantly increased the oxidation rate of additional applied S⁰. These stimulatory effects after the first applications of S⁰ were greater than those after two applications. The percent increase in S⁰ oxidation rate due to S⁰ pretreatment was negatively correlated with the oxidation capacities of soils before S⁰ pretreatments. The significant reduction of sulfur oxidation in autoclaved soils and significant increase in S⁰ oxidation after inoculation with S⁰-treated soil suspension demonstrated that microbial oxidation was mainly responsible for the enhancement of soil oxidation ability after previous S⁰ amendments.     

耕作方式对紫色水稻土全硫及有效硫的影响

以位于西南大学农业部重庆紫色土生态环境重点野外科学观测试验站 1990 年设立的长期免耕试验田为研究对象,通过采集 0 ~ 60 cm 土壤,应用等质量计算方法,探讨了冬水田平作（DP）、水旱轮作（SH）、垄作免耕（LM）和垄作翻耕（LF）等不同耕作方式对土壤全硫和有效硫的影响。结果表明,在 0 ~ 60 cm 深度内,土壤全硫和有效硫含量呈现出明显的垂直递减规律,即随着土壤深度的增加,含量逐渐降低;不同耕作方式下,土壤全硫含量及储量为 LM＞SH＞DP＞LF,有效硫含量及储量为 LM＞DP＞LF＞SH。长期垄作免耕提高了土壤全硫及有效硫的含量和储量,与对照 DP 处理相比,LM 处理全硫与有效硫含量分别增加了 20.80% 和 1.31%,储量分别增加了 19.54% 和 5.36%。耕作层（0 ~ 20 cm）,DP、SH、LM、LF 处理土壤有效硫平均含量分别为 27.15、13.45、31.43 和 24.01 mg/kg,DP、LF 以及 LM 处理为硫不缺或硫丰足,而 SH 处理为缺硫土壤（土壤有效硫含量＜16 mg/kg）。对缺硫土壤,应重视硫肥的施用,以促进农作物产量和品质的提高。     

A regional scale model for the calculation of episodic concentrations and depositions of acidifying components

An eulerian long-range transport model for the calculation of concentrations of SO₂, SO₄, NO _x , and NO₃ and wet and dry depositions of SO _x (sum of SO₂ and SO₄) and NO _y (sum of NO, NO₂ and NO₃) over Europe is presented. The model is developed in such a way that only routinely available, analyzed or prognostic meteorological fields are required as input data. In this way it is possible to obtain a forecast of the air quality during smog episodes. For evaluation of smog episodes the model provides a way to estimate the contributions of different sources and the effect of emission scenarios. The model has been evaluated for four winter and three summer episodes. The modeled concentrations of SO₂ and SO, are in agreement with the available measurements. A less good agreement is found for NO₂ and NO _x (sum of NO and NO₂) concentrations. For these components the model tends to underpredict the measured values.     

An automated turbidimetric method for total sulfur in plant tissue and sulfate sulfur in soils

Abstract

An automated turbidimetric method has been developed for the rapid and accurate determination of sulfate. The method is practical and useful for accurately measuring total sulfur in plant tissues, and extractable sulfate in soils. The principle of intermittent reagent addition is used which eliminates drift and sensitivity changes caused by coating of BaSO₄ on tubing and cell walls. Also, the appropriate chemistry is used to minimize interactions of the wash with the sample at a sampling rate of 30/H. The sensitivity of the method is excellent with a working range of 0 to 15 ppm sulfur for soils. For plant digests the sample solutions are diluted to 0–35 ppm S. The precision as determined by repeated analysis of a soil sample extract was 0.58% RSD with a mean of 9.26 pg/g extractable SO⁼ ₄‐S. On another soil sample using a different extractant and extraction procedure the RSD was 0.64%, mean of 9.26 μg/g. Multiple automated sulfur analyses on a plant tissue digest resulted in an RSD of 0.41% for a sample containing 0.21% S. The automated turbidimetric method for sulfate has excellent precision and sensitivity in plant tissue and soil analyses where gravimetric BaSO₄ assays are not practical.     

土壤中硫磺氧化的影响因素

通过综述影响硫磺氧化的土壤性质、肥料性质两部分内容,为进一步解决硫磺在土壤中氧化率低的问题,同时也为高效硫肥的研制提供理论依据。植物对于硫的需求日益增高,硫是作物必须的营养元素,被用来合成许多蛋白质和氨基酸,对植物的产量和品质有极大的影响,同时也在防治害虫、改良土壤性质方面发挥着巨大的作用。由于大气沉降、径流损失以及大量元素肥的过量施用导致硫元素附带输入减少和作物移除量的增加,土壤中硫含量供需不平衡,因此,硫肥添加成为未来的主流趋势。现有硫肥里的硫主要由两种形态组成,分别为单质态的硫磺和化合态的硫酸盐。硫磺廉价易得,在氧化过程中可以产生酸,改良碱性土壤pH,为更加科学地进行硫肥的研发设计,现需对硫磺在土壤里的主要氧化因素(微生物、pH、温度、湿度、粒径)进行系统的梳理。得到以下主要结论:微生物活性对硫磺的氧化作用要远大于数量,因此,影响微生物活性的土壤pH、温度、湿度等是极为重要的因素,微生物的种类在其中发挥的作用比重尚无绝对的定论。大多数研究表明,硫磺的氧化速率随土壤pH的降低而降低,在30～40℃且土壤含水量接近田间持水量时硫磺氧化速率最快。而硫磺粒径与氧化速率呈反比是确定的,其本质是微生物定殖于肥料颗粒的表面积起主导作用,并且受在土壤里的扩散影响,粉状硫磺相对于颗粒状硫磺更易于氧化。     

供硫水平对花生叶片硫素含量与形态的影响

采用盆栽方法研究了供硫水平对花生不同叶龄叶片的硫酸盐、谷胱甘肽和蛋白态硫含量及其形态的影响。结果表明,叶片谷胱甘肽含量随叶龄增大而减少,硫酸盐含量却相反。当硫素供应充足时,幼叶谷胱甘肽含量占总硫 4.6%,蛋白态硫含量占 91%,其余以硫酸盐形式存在;中龄叶及老叶的硫酸盐含量占总硫的60%~80%,而谷胱甘肽含量不到1%。当硫素供应不足时,幼叶和中龄叶含硫化合物总量减少,尤其是硫酸盐。因此,在缺硫时,谷胱甘肽不是植株硫的主要来源,且低氮加重缺硫症状发生。不同叶龄叶片对缺硫反应不同,幼叶对缺硫反应更为敏感。     

Climatological and Geographical Characteristics within Inversion Layers in the Presence of High NO2 Concentration

High concentrations of NO₂ may accumulate in the upper regions of the atmospheric inversion layers. In this study, the climatological and geographical characteristics of two cases where a high nighttime NO₂ concentration appeared in the inversion layer were studied, one on a slope on the Seto Inland Seacoast and in the Saijo Basin. On the Seto Inland Seacoast, the inversion layer appeared at 160 m a.s.l. There were remarkable differences in the concentration of NO₂ and saturation deficit across the boundary of the inversion layer. In Saijo Basin, the inversion layer covered almost the whole basin up to 500 m a.s.l. The cold air lake appearing below 290 m contained an especially high level of humidity and NO₂ concentration. In conclusion, it appears that the inversion layer plays a significant role as a cover preventing atmospheric NO₂ from diffusing outside the layer. In both cases, it seemed that the water vapor pressure almost reached saturation in the high NO₂ concentration zone.