Geostatistical characterization of nitrogen dioxide concentration in an urban area: Part II: Time component of the estimation error

The temporal component of the estimation error is usually neglected in calculation of the variance of the error associated with the mapping of annual nitrogen dioxide (NO₂) concentration. However, under realistic hypotheses, adding a temporal term to the spatial estimation variance is convenient enough. In a survey using passive diffusion samplers, which was carried out in 2001 on the Mulhouse area, the two measurement phases do not allow calculation of variance of the temporal error. But this error is accessible by means of the few fixed analyzers that continuously measure NO₂ concentrations. The statistics of the experimental temporal error are examined and the temporal variogram is calculated. Experimental quadratic error is then compared to the theoretical estimation variance, deduced from the temporal variogram.The fixed analyzers available in Alsace are then used to “optimize” empirically the duration and the date of the beginning of the temporary measurement phases.Without increasing the cost of the temporary survey, it is then possible to improve the precision of the maps of annual NO₂ concentration, by combining the spatial optimization presented in Part I of the paper, and the temporal optimization presented here.     

Effects of EDTA and low molecular weight organic acids on soil solution properties of a heavy metal polluted soil

A pot experiment was conducted to study the effects of EDTA and low molecular weight organic acids (LMWOA) on the pH, total organic carbon (TOC) and heavy metals in the soil solution in the rhizosphere of Brassica juncea grown in a paddy soil contaminated with Cu, Zn, Pb and Cd. The results show that EDTA and LMWOA have no effect on the soil solution pH. EDTA addition significantly increased the TOC concentrations in the soil solution. The TOC concentrations in treatments with EDTA were significantly higher than those in treatments with LMWOA. Adding 3 mmol kg(-1) EDTA to the soil markedly increased the total concentrations of Cu, Zn, Pb and Cd in the soil solution. Compared to EDTA, LMWOA had a very small effect on the metal concentrations. Total concentrations in the soil solution followed the sequence: EDTA > citric acid (CA) approximately oxalic acid (OA) approximately malic acid (MA) for Cu and Pb; EDTA > MA > CA approximately OA for Zn; and EDTA > MA > CA > OA for Cd. The labile concentrations of Cu, Zn, Pb and Cd showed similar trends to the total concentrations.     

Nitrous oxide emissions from tundra soil and snowpack in the maritime Antarctic

The nitrous oxide emissions were measured at three tundra sites and one snowpack on the Fildes Peninsula in the maritime Antarctic in the summertime of 2002. The average fluxes at two normal tundra sites were 1.1 ± 2.2 and 0.6 ± 1.7 μg N₂O m⁻² h⁻¹, respectively. The average flux from tundra soil site with penguin dropping addition was 3.7 ± 2.0 μg N₂O m⁻² h⁻¹, 3–6 times those from the normal tundra soils, suggesting that the deposition of fresh droppings enhanced N₂O emissions during penguin breeding period. The summer precipitation had an important effect on N₂O emissions; the flux decreased when heavy precipitation occurred. The diurnal cycle of the N₂O fluxes from Antarctic tundra soils was not obtained due to local fluky weather conditions. The N₂O fluxes through four snowpack sites were obtained by the vertical N₂O concentration gradient and their average fluxes were 0.94, 1.36, 0.81 and 0.85 μg N₂O m⁻² h⁻¹, respectively. The tundra soils under snowpack emitted N₂O in the maritime Antarctic and increased local atmospheric N₂O concentrations; therefore these fluxes could constitute an important part of the annual N₂O budget for Antarctic tundra ecosystem.     

Comparative chemical mass closure of fine and coarse aerosols at two sites in south and west Europe: Implications for EU air pollution policies

The chemical composition of PM10 and PM2.5 was studied during summer and winter sampling campaigns in South and West Europe (Barcelona, Spain, and Ghent, Belgium). The chemical composition of the PM10 aerosol was markedly different in the two regions, even at similar PM10 levels. The chemical composition of PM2.5 showed more similarities. The contribution of mineral matter was higher in Barcelona (on average 12% of the PM2.5 mass), whereas the contribution from sea salt was higher in Ghent (4% of PM2.5). Volatilisation of NH₄⁺ from the filters (negative artefact) was observed in both regions, although the extent of this artefact showed regional differences (0–4% and 22–38% of the NH₄⁺ mass in Ghent and Barcelona, respectively) and had no impact on the compliance with EU limit values. The number of exceedances of the PM10 limit value and an arbitrary PM2.5 limit of 25 μg m⁻³ was calculated by subtracting the mineral fraction (natural or anthropogenic in origin) from the bulk PM load, and this resulted in the elimination of the PM10 exceedances in Barcelona, and a reduction of one out of three exceedances in Ghent. The subtraction of sea-salt aerosol had no effect in Barcelona, and it removed one exceedance in each size fraction in Ghent. Exceedances of the PM10 daily limit value in Ghent coincided with back-trajectories originating from Eastern and Southern European regions. The origin of the exceedances in Barcelona during the campaigns was mostly local.     

Effect of cadmium on nodulation and N2-fixation of soybean in contaminated soils

The effects of cadmium stress on nodulation, N2-fixation capabilities of the root nodule, the change in ultrastructure of the root nodule, soybean growth, and the distribution of cadmium in plants were studied. The results obtained show that the nodulation of soybean roots was greatly inhibited by the addition of Cd, especially at the addition level of 10 and 20 mg kg(-1) soil. The inhibition of plant growth, especially the root growth, increased as the cadmium concentration increased, with deleterious effects observed for the roots. The weight ratio of soybean root/leaf decreased as the Cd concentration increased, which might explain the reason for nodulation decreases. The results also indicate that N2-fixation of root nodule was stimulated to some extent at the low levels of Cd addition, but decreased sharply with further increase of the Cd concentration. High Cd levels were also associated with changes in the ultrastructure of root nodule, in which the effective N2-fixing area was reduced and the N2-fixing cells in the area also reduced. In addition, the results also reveal that the content of Cd in different parts of the plants was as follows: roots > stems > seeds, indicating that the accumulation of Cd by roots is much larger than that by any other part of the soybean plant, and might cause deleterious effects to root systems.     

化学氧化剂对水华蓝藻的控制研究

对比了过氧化氢（H₂O₂）、高铁酸钾（K₂FeO₄）和过碳酸钠（Na₂CO₄）3种氧化剂对自然水体中群体蓝藻生长和光合活性的影响.结果发现,3种氧化剂对蓝藻均有快速的抑制效应,且随着氧化剂浓度的增加抑制效果增强.相同氧化剂浓度下,H₂O₂对水华蓝藻的去除能力强于K₂FeO₄和Na₂CO₄,对蓝藻光合系统Ⅱ的最大光量子产量（F_v/F_m）和有效光量子产量（F_v'/F_m'）的抑制效果也更显著.H₂O₂对不同浓度水华蓝藻的控制实验结果表明,初始藻细胞浓度对H₂O₂控藻效果影响较大,细胞密度越大,H₂O₂降解率增加,抑藻效果急剧下降.当初始藻密度为10μg/L和100μg/L,5mg/L H₂O₂的48h降解率分别为64.9%和97.5%,对藻细胞F_v/F_m的抑制率分别为10%和1%.因此,实施H₂O₂控制蓝藻水华的措施应该尽量在蓝藻水华形成早期,即藻密度较低的时候使用.     

长江三角洲晚第四纪陆-海交互地层的光释光年代学

长江三角洲地层的年代学研究对探讨晚第四纪以来我国东部沿海地区陆海交互作用历史以及海岸地貌的形成与演化具有重要价值。本研究选择长江三角洲YZ07和EGQD14两支钻孔开展系统光释光（optically stimulated luminescence,OSL）测年研究,总结前期已发表的50个年代数据并收集整理该区域相关钻孔的年代地层资料,探讨在可靠的年代框架约束下晚第四纪长江三角洲沉积地层演变特征,取得了以下几点认识：（1）在长江三角洲地区,常规OSL测年以较细石英颗粒OSL测年效果较为理想;对粗颗粒石英,若存在长石包裹体对石英OSL信号的影响,建议用脉冲释光测年（POSL）技术加以解决。（2）以YZ07孔为例,¹⁴C测年和OSL测年结果对比表明在三角洲海岸地区,¹⁴C测年方法建立的年代地层框架需要谨慎对待,建议在此区域开展年代地层学研究时可以尝试将两种测年方法结合使用,以确保年代地层框架的准确和可靠。（3）针对争议较大的氧同位素3阶段（MIS3）沉积环境问题,EGQD14孔给出了新的年代学证据,认为MIS3阶段（约30?—?50 ka）长江三角洲可能是陆地河流相沉积环境为主导,这也得到了区域相邻的几支钻孔沉积记录的佐证。（4）两支钻孔从年代学角度证实了前人关于末次盛冰期（Last Glacial Maximum,LGM）以来长江三角洲发育下切河谷的沉积学判识和地层学论断。此外,多钻孔的年代地层学特征也验证了全新世时段海平面变化控制下的长江三角洲及海岸演变的时空动态。     

太湖北部湖区春、冬季节天然有机质的荧光特征及环境意义

天然有机质(OM)广泛存在于各类水体,含有丰富的碳、氮、磷等生源要素,其形成、转化、归宿及其相伴随的营养盐再生过程是水生态系统营养盐生物地球化学循环的重要环节,在湖泊蓝藻水华暴发过程中势必也扮演着非常重要的营养盐供给者的角色.本研究于2015年2月和5月分别在太湖北部湖区采集了17个样品,利用POM-DOM PARAFAC三维荧光模型解析春、冬季节颗粒态有机质(POM)和溶解态有机质(DOM)的荧光特征及来源,并探讨POM和DOM各荧光组分之间及其与叶绿素a(Chla)的关系.结果表明,春、冬季节太湖北部湖区POM和DOM的荧光峰、荧光中心位置和荧光强度均存在明显的差别;POM有着比DOM更复杂的组分构成.综合POM和DOM的荧光强度和荧光指数可知,春、冬季节太湖北部湖区POM和DOM均以自生源为主,河口区受陆源贡献较大.POM(C1p~C5p)和DOM(C1d~C5d)有5种荧光组分,分别是类色氨酸(C1和C2)、类腐殖质(C3和C4)及类酪氨酸(C5).POM和DOM的荧光组分特征存在明显的差别;春、冬季节POM均以类腐殖质荧光C3为主,荧光组分高值区分别集中在梅梁湾区域和湖心区;而DOM均以类蛋白组分C2、C1和C5为主,荧光组分高值区均分布在竺山湾区域.相关分析结果显示,春季C1d与C2d(P0.01)、C3d与C4d(P0.01)、C1p与C4p(P0.05)、C2p与C5p(P0.01)均具有较强的相关性.值得注意的是,C3d(P0.01)、C4d(P0.05)与C3p均具有较好的相关关系,表明POM与DOM在组分、来源上具有某种联系.与春季类似,冬季荧光组分C1d与C2d、C3d与C4d、C1p与C2p、C1d与C2p亦具有极好的相关性(P0.01).春季C5d与Chla之间存在正相关关系(P0.01),而C2d(P0.05)、C3p(P0.01)与Chla之间具有负相关关系;冬季C4d与Chla之间也存在负相关关系(P0.05).     

厌氧条件下可溶性有机质对汞的还原与氧化作用

在沉积物、湿地和淹水的水稻土中天然可溶性有机质(DOM),如胡敏酸(HA)和富里酸(FA)处于还原状态,其介导Hg(Ⅱ)的还原,影响汞的转化及地球化学循环.本文通过模拟黑暗厌氧环境,研究还原态HA与FA对Hg(Ⅱ)的还原.结果表明,还原态HA与FA的还原容量高于对照氧化态HA与FA.还原态HA与FA对Hg(Ⅱ)的还原最佳浓度分别是0. 2mg·L~(-1)和1. 5 mg·L~(-1).而高于最佳浓度时,由于发生巯基竞争性络合作用,抑制Hg(Ⅱ)的还原;特别是还原态HA大于5mg·L~(-1)时,不能还原Hg(Ⅱ)为Hg(0).还原态HA与FA对Hg(Ⅱ)的还原反应动力学表明:有机碳(DOC)与Hg(Ⅱ)摩尔比DOC∶Hg(Ⅱ)=400∶1时,还原反应速率IHSS-HA FRC-HA FRC-FA;高摩尔比[DOC∶Hg(Ⅱ)=10 000∶1]时,还原态HA对Hg(Ⅱ)的还原反应停止,甚至向相反方向进行.还原态HA与FA对Hg(0)氧化结果表明,当还原态HA与FA浓度分别增加至5 mg·L~(-1)和10 mg·L~(-1)时,样品中检测不到Hg(0),还原态HA与FA对Hg(0)发生诱导性氧化络合作用.在汞的氧化还原与络合作用中,还原态DOM扮演双重角色,影响活性汞的可利用性,进而影响微生物汞的甲基化.     

于桥水库沉积物-水界面氮磷剖面特征及交换通量

于桥水库是天津市重要的饮用水源地,但近年来呈现富营养化加重趋势,而其内源负荷及污染分布特征尚不清楚.本研究利用Peeper(pore water equilibrium)技术获取沉积物-水界面氮磷剖面特征,分析于桥水库间隙水氮磷分布的空间差异;采集沉积物无扰动柱样分析沉积物中易释放态氮及磷的赋存特征,并利用原柱样静态培养法对其水土界面氮磷交换速率进行估算.结果表明:(1)沉积物中活性磷、氨氮、硝态氮和亚硝态氮的含量分别为0.5~6.5、0.5~10.9、2.2~16.2和0.05~0.6 mg·kg~(-1),在垂直方向随深度增加营养盐含量降低,而在空间分布上差异显著.(2)上覆水中PO_4~(3-)-P和NH_4~+-N质量浓度较低,间隙水中PO_4~(3-)-P和NH_4~+-N质量浓度远大于上覆水,表明于桥水库间隙水具有向上覆水体扩散营养盐的潜力.在垂直方向上间隙水中PO_4~(3-)-P和NH_4~+-N具有在0~5 cm快速增加,之后表现出逐渐降低的趋势.(3)静态释放结果表明,PO_4~(3-)-P和NH_4~+-N从沉积物间隙水扩散至上覆水中,其释放通量分别为1.1~13.3 mg·(m~2·d)~(-1)和20.6~250.5 mg·(m~2·d)~(-1);NO-3-N交换通量在-20.4~33.4 mg·(m~2·d)~(-1)之间,NO_2~--N交换通量在-7.4~0.4 mg·(m~2·d)~(-1)之间.PO_4~(3-)-P和NH_4~+-N为于桥水库主要的沉积物内源向上覆水释放营养盐,总体释放速率在空间上呈现南高北低、淋河口和水坝前较高的释放特征.与类似研究比较可知,于桥水库沉积物-水界面通量相对较高,表明沉积物是于桥水库上覆水营养盐的重要来源.