珠三角地区大气PM_(2.5)理化特性季节规律与成因

基于珠三角大气超级站2013年8月至2014年3月PM2.5、PM2.5中主要水溶性无机离子组分及其重要气态前体物等参数的逐时在线监测结果,揭示当地大气PM2.5中二次无机组分与其气态前体物的相互作用,以及PM2.5理化特性与成因的季节差异。结果表明,观测期间,PM2.5、PM10的年平均质量浓度分别为64.2、105.1μg/m3,PM2.5在PM10中所占比例(PM2.5/PM10)平均为61.1%。SO2-4、NO-3、NH+4的年平均质量浓度分别为16.6、9.0、10.2μg/m3,3者之和(SNA)占PM2.5的比例(SNA/PM2.5)平均为55.8%,体现了二次转化对珠三角地区PM2.5污染的重要影响;不同季节,SNA/PM2.5为46.0%~64.3%,夏季最低,冬季最高,其中SO2-4、NH+4对PM2.5的贡献相对稳定,NO-3贡献的季节差异较大;秋、冬季各项观测参数浓度的日变化规律相对明显,夏季除HNO3和NH3外,多项观测参数在低浓度水平波动,日变化规律不明显;珠三角大气中具有足量气态NH3以中和硫酸盐和硝酸盐,PM2.5中NH+4、SO2-4、NO-3主要以(NH4)2SO4和NH4NO3形式存在;本研究站点夏季的硫氧化率和氮氧化率均高于广州市,这充分体现了该站点的区域性特征。     

磷酸活化-微波热解改性污泥对镉的吸附性能

以城市污水处理厂剩余污泥为原料,利用磷酸活化-微波热解制取改性污泥。以此污泥作为吸附剂,对含Cd2+废水进行了吸附实验研究。考察了溶液反应时间、Cd2+浓度、pH值和吸附剂用量对镉吸附去除效果的影响;利用等温吸附实验作出吸附等温线,并考察了改性污泥吸附剂吸附Cd2+的动力学方程。实验结果表明,改性污泥对Cd2+有良好的吸附性能,吸附最佳pH值为6.0,吸附较好地符合一级动力学吸附模型和Langmuir-Freundlich等温吸附方程,吸附为物理吸附,吸附反应发生12 h后达到吸附平衡。     

矸石基X型分子筛对水中Co2+、Cu2+、Cd2+和Cr3+的去除

以煤矸石为原料,采用碱熔后水热合成法制备X型分子筛并进行XRD、SEM、BET和Zeta电位分析。研究其对水中Co2+、Cu2+、Cd2+和Cr3+4种离子的吸附性能,包括吸附等温线、吸附动力学以及初始金属离子浓度、pH值对吸附性能的影响。所合成的矸石基X型分子筛的BET比表面积为676.02 m2/g,微孔孔容为0.263 cm3/g。吸附实验表明,矸石基X型分子筛能有效去除上述4种离子,同时实现煤矸石的资源化和金属离子的去除。4种离子的平衡吸附量均随初始浓度的增大而增大,相同条件下平衡吸附量的大小顺序为Cd2+>Cr3+>Cu2+>Co2+。准二级动力学模型能很好地描述4种离子的吸附动力行为。Langmuir模型对Co2+、Cu2+和Cd2+吸附的拟合较Freundlich模型高,说明其主要表现为物理吸附过程。4种离子的吸附速率均由液膜扩散和颗粒内扩散共同控制。     

Enhanced resistance of yeast mutants deficient in low-affinity iron and zinc transporters to stannous-induced toxicity

Tin or stannous (Sn²⁺) compounds are used as catalysts, stabilizers in plastic industries, wood preservatives, agricultural biocides and nuclear medicine. In order to verify the Sn²⁺ up-take and toxicity in yeast cells we utilized a multi-elemental analysis known as particle-induced X-ray emission (PIXE) along with cell survival assays and quantitative real-time PCR. The detection of Sn²⁺ by PIXE was possible only in yeast cells in stationary phase of growth (STAT cells) that survive at 25 mM Sn²⁺ concentration. Yeast cells in exponential phase of growth (LOG cells) tolerate only micro-molar Sn²⁺ concentrations that result in intracellular concentration below of the method detection limit. Our PIXE analysis showed that STAT XV185-14c yeast cells demonstrate a significant loss of intracellular elements such as Mg, Zn, S, Fe and an increase in P levels after 1 h exposure to SnCl₂. The survival assay showed enhanced tolerance of LOG yeast cells lacking the low-affinity iron and zinc transporters to stannous treatment, suggesting the possible involvement in Sn²⁺ uptake. Moreover, our qRT-PCR data showed that Sn²⁺ treatment could generate reactive oxygen species as it induces activation of many stress-response genes, including SOD1, YAP1, and APN1.     

百色市右江区大气PM10中水溶性无机离子的化学特征与来源

2010年10月至2011年9月采集百色市右江区大气PM10样品,分析PM10及其水溶性无机离子的化学特征与来源。结果表明:(1)百色市右江区大气PM10为13.89～319.44μg/m3,年均117.48μg/m3,年均值超过《环境空气质量标准》(GB 3095-2012)二级标准(100μg/m3)。百色市右江区大气可吸入颗粒物的污染主要出现在春冬季节。(2)水溶性无机离子浓度年均值依次为SO24->NO3->Cl->NH4+>K+>Na+>Mg2+>F-,SO24-、NO3-和Cl-浓度最高,分别占水溶性无机离子的57.7%、14.9%和14.5%。(3)百色市右江区大气PM10呈较强的酸性,高浓度的SO42-可能是导致百色市右江区大气PM10呈较强酸性的主要原因。(4)PM10的季节变化受气温和风速的影响极显著;气象因素对SO42-、NO3-、F-的影响不显著。(5)主因子分析表明,PM10中水溶性无机离子可能来自3个方面,Cl-和NO3-主要来自于当地低烟卤煤燃烧排放的烟气;Mg2+、K+和Na+主要来自于自然源;F-、SO24-和NH4+主要来自于混合源。     

改性多壁碳纳米管对水中Cd~（2＋）的去除

为了增加多壁碳纳米管（multiwall carbon nanotubers,MWNTs）对水中Cd2＋的吸附量,使用混酸对多壁碳纳米管进行氧化处理,采用红外光谱进行结果表征,并探讨了吸附时间、pH值和MWNTs的使用量、Cd2＋的浓度及干扰离子对镉离子吸附的影响。结果表明,吸附时间为1.5 h、pH为5.3、吸附效果最佳,随MWNTs量的增加Cd2＋去除量增加,共存的阳离子会降低对Cd2＋的吸附效果,对Cd2＋的吸附符合Longmuir吸附定律。研究同时表明,pH小于2时Cd2＋能容易从碳纳米管上解吸。初步探讨了Cd2＋吸附机制。     

TiO_2/EP光催化降解水体中微污染磺胺嘧啶的研究

制备了膨胀珍珠岩(EP)为载体的TiO2催化剂(TiO2/EP),对使用较为广泛的抗生素磺胺嘧啶(SDZ)进行了光催化降解研究,探讨了TiO2的负载量、溶液的初始浓度、初始pH、无机离子(HCO3-、SO42-和Cl-)和腐殖酸(HA)对SDZ降解效果的影响。结果表明:SDZ的光催化降解符合一级反应动力学方程;当TiO2最佳负载量为20 wt%,SDZ浓度为5 mg/L,pH=6.7,紫外光照射强度为1 000μW/cm2,反应时间为45 min时,SDZ的降解率达到96%;HCO3-在低浓度时能促进SDZ的光催化降解,高浓度时促进作用不明显;SO42-和Cl-对SDZ的光催化降解有轻微的抑制作用;HA对SDZ光催化降解有显著的抑制作用,浓度越高,抑制作用越强。UV-TiO2/EP是一种去除水体中微污染SDZ的有效方法。     

Effects of Soil Amendments at a Heavy Loading Rate Associated with Cover Crops as Green Manures on the Leaching of Nutrients and Heavy Metals from a Calcareous Soil

The potential risk of groundwater contamination by the excessive leaching of N, P and heavy metals from soils amended at heavy loading rates of biosolids, coal ash, N‐viro soil (1:1 mixture of coal ash and biosolids), yard waste compost and co‐compost (3:7 mixture of biosolids to yard wastes), and by soil incorporation of green manures of sunn hemp (Crotalaria juncea) and sorghum sudangrass (Sorghum bicolor × S. bicolor var. sudanense) was studied by collecting and analyzing leachates from pots of Krome very gravelly loam soil subjected to these treatments. The control consisted of Krome soil without any amendment. The loading rate was 205 g pot^? 1 for each amendment (equivalent to 50 t ha^? 1 of the dry weight), and the amounts of the cover crops incorporated into the soil in the pot were those that had been grown in it. A subtropical vegetable crop, okra (Abelmoschus esculentus L.), was grown after the soil amendments or cover crops had been incorporated into the soil. The results showed that the concentration of NO₃‐N in leachate from biosolids was significantly higher than in leachate from other treatments. The levels of heavy metals found in the leachates from all amended soils were so low, as to suggest these amendments may be used without risk of leaching dangerous amounts of these toxic elements. Nevertheless the level of heavy metals in leachate from coal ash amended soil was substantially greater than in leachates from the other treatments. The leguminous cover crop, sunn hemp, returned into the soil, increased the leachate NO₃‐N and inorganic P concentration significantly compared with the non‐legume, sorghum sudangrass. The results suggest that at heavy loading rates of soil amendments, leaching of NO₃ ^? could be a significant concern by application of biosolids. Leaching of inorganic P can be increased significantly by both co‐compost and biosolids, but decreased by coal ash and N‐viro soil by virtue of improved adsorption. The leguminous cover crop, sunn hemp, when incorporated into the soil, can cause the concentration of NO₃‐N to increase by about 7 fold, and that of inorganic P by about 23% over the non‐legume. Regarding the metals, biosolids, N‐viro soil and coal ash significantly increased Ca and Mg concentrations in leachates. Copper concentration in leachate was increased by application of biosolids, while Fe concentration in leachates was increased by biosolids, coal ash and co‐compost. The concentrations of Zn, Mo and Co in leachate were increased by application of coal ash. The concentrations of heavy metals in leachates were very low and unlikely to be harmful, although they were increased significantly by coal ash application.     

Is the bone tissue of ring-billed gulls breeding in a pollution hotspot in the St. Lawrence River,Canada, impacted by halogenated flame retardant exposure?

Bone metabolism is a tightly regulated process that controls bone remodeling and repair in addition to maintaining circulating calcium and phosphate levels. It has been shown that certain organohalogen contaminants may adversely impact bone tissue metabolism and structure in wildlife species. However, exceedingly few studies have addressed the bone-related effects of organohalogen exposure in birds. The objective of the present study was to investigate the associations between markers of bone metabolism and structural integrity, and concentrations of established and current-use halogenated flame retardants (FRs) in ring-billed gulls (Larus delawarensis) nesting in a known FR hotspot area in the St. Lawrence River (Montreal, Canada). Bone metabolism was assessed using plasma calcium and inorganic phosphate levels, and alkaline phophatase activity, while bone (tarsus; trabecular and cortical sections) structure quality was examined using the percentage of bone tissue comprised in the total bone volume (Bv/Tv) and bone mineral density (BMD). Bv/Tv and BMD of the tarsus tended (not significant) to be positively associated with circulating calcium levels in male ring-billed gulls. Moreover, concentrations of FRs in male bird liver (brominated diphenyl ether (BDE)-154, -183, -201, and -209) and plasma (BDE-209) were negatively correlated with trabecular and cortical BMD of the tarsus. These correlative associations may suggest light demineralization of bone tissue associated with FR exposure in male ring-billed gulls. Present findings provide some evidence that bone (tarsus) metabolism and mineral composition may be impacted in high FR-exposed (mainly to PBDEs) ring-billed gulls breeding in the highly urbanized Montreal region.     

Development and application of LC–APCI–MS method for biomonitoring of animal and human exposure to imidacloprid

Imidacloprid (IMI) is a relatively new neuro-active neonicotinoid insecticide and nowadays one of the largest selling insecticides worldwide. In the present study a LC–APCI–MS based method was developed and validated for the quantification of imidacloprid and its main metabolite 6-chloronicotinic acid (6-CINA) in urine and hair specimens. The method was tested in biomonitoring of intentionally exposed animals and subsequently applied for biomonitoring of Cretan urban and rural population.