水稻土中铁-氮循环耦合体系影响镉活性机理研究

关于铁-氮循环耦合体系对镉(Cd)活性影响的研究目前尚鲜见报道.本文采用淹水培养试验,研究不同硝酸根(NO_3~-)、铵根(NH_4~+)处理条件下,南方典型Cd污染水稻土中铁氧化还原与氮形态转化耦合关系及其对Cd活性影响的机理.结果表明:随着培养时间延长,不同处理的pH值逐渐向7.0靠拢,Eh值由273~321 mV持续下降至118~132 mV,pe+pH值(e-活度的负对数值与H+活度的负对数值之和)从10.62~11.19持续下降至8.55~8.83,土-水体系处于中度还原条件;化学反硝化(Chemodenitrification)和NO_3~-依赖的厌氧铁氧化过程(Microbial NO_3~--dependent FeIIoxidation,NDFO)生成无定形氢氧化铁(Fe(OH)_3(amorp)),其对Cd~(2+)专性吸附及与Cd~(2+)共沉淀降低了有效态Cd浓度,加之pH值上升增大Cd~(2+)在土壤固相表面的吸附量,导致水稻土中Cd活性下降;NH_4~+被Fe(OH)_3(amorp)厌氧氧化(Anaerobic NH_4~+oxidation coupled to FeIII reduction,Feammox)会消耗H+而提高体系的pH值,在一定程度上会降低Cd活性,但其自身与Cd~(2+)对土壤固相表面吸附位点的竞争,可能会更大程度地减少Cd~(2+)在土壤固相表面的吸附量,而导致Cd活性提高.本研究成果可为丰富和拓展水稻土中Cd的生物地球化学理论,并为南方Cd污染农田修复及治理提供科学依据.     

高级氧化法去除水中药物和个人护理用品的研究进展

药品和个人护理用品(PPCPs)由于其对环境及人体具有潜在影响,受到国内外越来越多的关注。高级氧化技术(AOPs)对于处理PPCPs极具发展前景。本文概括了药品和个人护理用品(PPCPs)的概念和种类,并对几种高级氧化技术处理PPCPs的基本原理和处理效果做了较为详细的阐述并提出进一步可能的研究方向。     

Identification of anthropogenic effects and seasonality on water quality in Daya Bay, South China Sea

Thirteen water quality parameters from 12 monitoring stations were collected to study the effects caused by climate and anthropogenic activities on water quality in 2003 in Daya Bay, South China Sea. The data matrix has been built according to the results, which were analyzed by fuzzy c-mean cluster (FCM) and cluster analysis (CA). This analysis has identified anthropogenic effects and seasonal characters of water quality. The dry and wet seasonality have been demonstrated with FCM and CA. The precipitation and the Southeast Asian monsoons, northeasterly from October to the next April and southwesterly from May to September have also an important influence on water quality in Daya Bay. In the spatial pattern, two groups have been classified with FCM and CA. Cluster I consisted of the sites S3, S8, S10 and S11 in the west and north coastal parts of Daya Bay. Cluster I is mainly related to anthropogenic activities such as fish-farming. Cluster II consisted of the rest of the stations in the center, east and south parts of Daya Bay. Cluster II is mainly related to seawater input from South China Sea. Thus, fuzzy c-mean cluster and cluster analysis can be an important tool for the successful characterization of regional-scale water quality.     

Secondary organic aerosols in Jinan, an urban site in North China: Significant anthropogenic contributions to heavy pollution

Secondary organic aerosols(SOAs) are an important component of particulates, but whether biogenic SOAs(BSOAs) or anthropogenic SOAs(ASOAs) are the dominant contributors to haze pollution remains poorly characterized. In this study, particulate samples were collected from September 2014 to August 2015 at an urban site in Jinan, which is the capital of Shandong Province and a typical city in the North China Plain. The PM2.5 samples were analyzed for BSOA(isoprene(SOAI) and monoterpenes(SOAM)) and ASOA(aromatic(SOAA)) tracers. The concentrations of the SOAAtracer(1.1 ± 1.0 ng/m3) were lowest, and those of SOAItracers(41.8 ± 86.2 ng/m3) were highest, with the concentrations of SOAMtracers(19.4 ± 9.9 ng/m3) being intermediate. The SOAItracers were more abundant in the summer and less abundant in the winter. Both SOAIand SOAMincreased with increasing ozone level but decreased with increasing NOx level. Correlation analysis revealed a good correlation between 2,3-dihydroxy-4-oxopentanoic acid and levoglucosan levels in three seasons. These results suggested that biomass burning activities occurring in the NCP can enhance the emissions of aromatics and should be controlled, especially in the autumn and winter. SOA tracers were classified according to pollution degree, and the results showed that as pollution increases, the contributions of SOAAincrease. These results indicate that reducing anthropogenic emissions is necessary to prevent SOA pollution, especially during heavy pollution episodes.     

不同植被下土壤碳转移对岩溶动力系统中碳循环的影响

土壤是陆地生物生长、发育、繁殖的最佳场所,也是岩溶发育最为活跃的部位。土壤～岩石(土箱)、草本植物(麦冬)-土壤-岩石(草箱)、木本植物(黄杨)-土壤-岩石(树箱)体系中碳循环的模拟试验显示,黄杨具有较大的树冠可截获更多的降雨,根系的呼吸作用、分泌作用和土壤微生物活力的提高,使土壤环境中CO2浓度提高,树箱比土箱、草箱分别提高148.08%、75.01%,而土壤呼吸排放CO2的量则分别提高175.75%、171.14%;随水排泄的无机碳浓度分别提高77.78%、72.49%,排泄的总量分别提高166.49%、153.81%。碳循环强度的增加,使土下碳酸盐岩的侵蚀能力加强,树箱比土箱提高2.84倍、比草箱提高1.36倍。     

Molecular characterisation of the dissolved organic matter of wastewater effluents by MSSV pyrolysis GC-MS and search for source markers

Microscale sealed vessel pyrolysis (MSSVpy) was used to characterise the hydrophobic (HPO) and colloid (COL) fractions of dissolved organic matter (DOM) from the effluents (EFFs) of two waste water treatment plants (WWTPs) and several primary source waters (SWs). The EFFs showed a large range of anthropogenically sourced organics - including the metabolites of industrial chemicals (e.g., dioxanes, n- and sec-alkyl substituted benzenes and long chain alkyl phenols), pharmaceuticals (e.g., N- and S-heterocycles) and human waste (e.g., S- and N-organics, steranes/sterenes) - as well as high concentrations of alkyl aromatic and N-organic products (e.g., alkyl indoles, carbazoles and β-carbolines) attributed to the treatment biota. Some anthropogenic chemicals are potentially toxic at even trace levels, whilst the N-organics may be precursors for toxic N-disinfection by-products. Much lower concentrations of just a few of the anthropogenic and N-organic products were detected by more traditional flash pyrolysis (Flash-py) of the EFF samples, reflecting the higher sensitivity of MSSVpy to many chemical functionalities. Few of these products were detected in the corresponding MSSVpy analysis of the SWs, but these samples did show relatively high abundances of lignin (e.g., alkylphenols) and carbohydrate (e.g., furans) derived products. Their lower EFF abundances are consistent with efficient removal by the water treatment procedures applied. Conversely, the detection of the anthropogenics in the treated EFFs reflects their general resistance to treatment. Their occurrence in the HPO fractions isolated by XAD resin separation suggests a potential relationship with the structurally stable macromolecular fraction of the DOM.     

Real-time wet scavenging of major chemical constituents of aerosols and role of rain intensity in Indian region

Real-time simultaneous studies on chemical characteristics of rainwater and PM₁₀ aerosols were carried out to understand the scavenging of major chemical components in Indian region. The concentrations of Ca²⁺, NH₄⁺, SO₄²⁻ and NO₃⁻ were observed to be lower in the aerosol samples collected during rain as compared to before and after rain events. The most significant reduction was noticed for Ca²⁺ (74%) during rain which showed highest scavenging ratio (SR) and indicated that below-cloud scavenging is an effective removal process for Ca²⁺ in Indian region. Among non-sea salt components, Ca²⁺ had highest SR at Hyderabad indicating typical characteristics of crustal influence as abundance of calcium carbonate in soil dust has been reported in India. However, the levels of these major chemical components gradually got build-up in due course of time. After rain events, the levels of SO₄²⁻ aerosols were noticed to be substantially higher (more than double) within 24 h. In general, scavenging ratios for all components (except Ca²⁺, NH₄⁺ and K⁺) were higher over BOB as compared to Hyderabad. The maximum fall in aerosol levels (BR minus AR) was observed during continuous and low intensity rain events that did not allow building up of aerosol concentrations.     

Experimental study and steady-state simulation of biogeochemical processes in laboratory columns with aquifer material

Packed bed laboratory column experiments were performed to simulate the biogeochemical processes resulting from microbially catalyzed oxidation of organic matter. These included aerobic respiration, denitrification, and Mn(IV), Fe(III) and SO(4) reduction processes. The effects of these reactions on the aqueous- and solid-phase geochemistry of the aquifer material were closely examined. The data were used to model the development of alkalinity and pH along the column. To study the independent development of Fe(III)- and SO(4)-reducing environments, two columns were used. One of the columns (column 1) contained small enough concentrations of SO(4) in the influent to render the reduction of this species unimportant to the geochemical processes in the column.The rate of microbially catalyzed reduction of Mn(IV) changed with time as evidenced by the variations in the initial rate of Mn(II) production at the head of the column. The concentration of Mn in both columns was controlled by the solubility of rhodochrosite (MnCO(3(S))).In the column where significant SO(4) reduction took place (column 2), the concentration of dissolved Fe(II) was controlled by the solubility of FeS. In column 1, where SO(4) reduction was not important, maximum dissolved Fe(II) concentrations were controlled by the solubility of siderite (FeCO(3(S))). Comparison of solid-phase and aqueous-phase data suggests that nearly 20% of the produced Fe(II) precipitates as siderite in column 1. The solid-phase analysis also indicates that during the course of experiment, approximately 20% of the total Fe(III) hydroxides and more than 70% of the amorphous Fe(III) hydroxides were reduced by dissimilatory iron reduction.The most important sink for dissolved S(-II) produced by the enzymatic reduction of SO(4) was its direct reaction with solid-phase Fe(III) hydroxides leading initially to the formation of FeS. Compared to this pathway, precipitation as FeS did not constitute an important sink for S(-II) in column 2. In this column, the total reacted S(-II) estimated from the concentration of dissolved sulfur species was in good agreement with the produced Cr(II)-reducible sulfur in the solid phase. Solid-phase analysis of the sulfur species indicated that up to half of the originally produced FeS may have possibly transformed to FeS(2).     

The Behaviour of Selenium in Geological Processes

Selenium contents were analyzed from a total of 244 soil samples collected over different rock types at a sampling density of one sample per 4km² around Geita gold mining areas, Northwestern Tanzania. Comparisons using literature survey contents of selenium in geological materials and some implications on the selenium in soils are compiled and discussed. Most selenium occurs as simple selenides in small quantities in low temperature hydrothermal deposits devoid of sulphur. It has been observed that to a large extent selenium content is increased more than most trace elements in the upper parts of the Earth perhaps through extraterrestrial deposition. In deep-seated rocks selenium is associated with sulphur but being volatile selenium and sulphur do not behave according to the crystallochemical law. Due to the higher stability of S⁶⁺, Se⁴⁺ and Se⁰ separate during migration. Thus, selenium is especially found in deep-seated plutonic rocks where large magma bodies cooled slowly and sulphur is available to precipitate sulphides. Selenium, which occurs with sulphides, is inhomogeneously deposited into continental margins. It is increased during magmatic differentiation and is highest in basic rocks. In magmatic and metamorphic conditions, selenium is found in the crystal structures of sulphides while in pneumatolytic and hydrothermal processes, it is relatively enriched into the late differentiates compared to sulphur. In metamorphic rocks selenium is more widely distributed. Selenium content in soils in the investigated area varies from (0.3–0.5gg^–1) in laterite and in black cotton soil 0.4gg^–1. Of all volcanic rocks selenium is highest in volcanogenic rocks especially the basalts. Surface waters are enriched in selenium, which they leach from volcanic materials. Selenium in sediments containing clay and organic matter is elevated but the content decreases with increased metamorphism. Selenium in volcanic areas can be used as a pathfinder in prospecting for volcanogenic ore deposits. S/Se ratios are distinct in different rock types and can thus be used to elucidate the origin of rocks, ores, and sediments.     

Differences of the oxidation process and secondary organic aerosol formation at low and high precursor concentrations

Current atmospheric quality models usually underestimate the level of ambient secondary organic aerosol(SOA), one of the possible reasons is that the precursors at different concentrations may undergo different oxidation processes and further affect SOA formation. Therefore, there is a need to perform more chamber studies to disclose the influence. In this work, SOA formation over a wide range of initial precursor concentrations(tens of ppb to hundreds of ppb levels) was investigated in a 30 m3 indoor smog chamber,and mainly through the analysis of multiple generations of VOCs detected from HR-To FPTRMS to expound the difference in the oxidation process between low and high precursor concentrations. Compared to high initial concentrations, gas-phase intermediates formed at low concentrations had a higher intensity by about one order of magnitude, and the lowvolatility compounds also had a higher formation potential due to the competition between semi-volatile intermediates and precursors with oxidants. In addition, the formed SOA was more oxidized with higher f44 value(0.14 ± 0.02) and more relevant to real atmosphere than that formed at high concentrations. This work should help to deeply understand SOA formation and improve the performance of air quality models for SOA simulation.