基于TEM-EDS对四川盆地大气单颗粒气溶胶的研究

为了解四川盆地大气中单颗粒气溶胶理化特征,分别在该区域典型城市（成都市）和背景地区（峨眉山）进行了大气单颗粒样品采集.基于带能谱的透射电子显微镜（TEM-EDS）对两地累计3923个单颗粒的化学组成、形貌特征及混合状态等进行了全面观测和分析,并对两地颗粒物差异性进行了对比分析.结果发现：两地气溶胶颗粒主要包括有机物、富硫、矿物、烟尘和飞灰/金属颗粒,除了以单独的外混形式存在外,大多数颗粒以两种及两种以上颗粒类型混合（即内混）形式存在.通过对成都市不同污染状况下单颗粒特征对比发现,"污染天"的内混颗粒占比高于"清洁天",分别为74.2%和68.6%;相比"清洁天","污染天"颗粒物粒径分布范围更广且峰值区间更大,表明污染过程中颗粒物的大气混合趋于更强.对比成都市与峨眉山分析结果得知,成都市以内混的有机物-硫颗粒为主导（占比为50.2%）,而峨眉山以外混的有机物颗粒为主导（占比为50.5%）;成都市含硫类颗粒物（如有机物-硫颗粒）贡献高于峨眉山,而峨眉山两种含碳类颗粒（如烟尘和有机物-烟尘颗粒）占比高于成都市;此外,成都市与峨眉山两地大气颗粒物粒径分布范围及峰值区间均存在一定差异,进一步体现了两地颗粒物来源和老化混合的差异.在峨眉山,与非降雨天相比,一些易溶于水的颗粒物（如含硫类颗粒）在降雨天占比明显降低,而源自当地燃烧过程、粒径较小且疏水性强的颗粒物（如烟尘和有机物-烟尘颗粒）占比相应升高.     

Comprehensive and high-resolution emission inventory of atmospheric pollutants for the northernmost cities agglomeration of Harbin-Changchun, China: Implications for local atmospheric environment management

Using a bottom-up estimation method, a comprehensive, high-resolution emission inventory of gaseous and particulate atmospheric pollutants for multiple anthropogenic sectors with typical local sources has been developed for the Harbin-Changchun city agglomeration (HCA). The annual emissions for CO, NOx, SO₂, NH₃, VOC_S, PM_2.5, PM₁₀, BC and OC during 2017 in the HCA were estimated to be 5.82 Tg, 0.70 Tg, 0.34 Tg, 0.75 Tg, 0.81Tg, 0.67 Tg, 1.59 Tg, 0.12 Tg and 0.26 Tg, respectively. For PM₁₀ and SO₂, the emissions from industry processes were the dominant contributors representing 54.7% and 49.5%, respectively, of the total emissions, while 95.3% and 44.5% of the total NH₃ and NOx emissions, respectively, were from or associated with agricultural activities and transportation. Spatiotemporal distributions showed that most emissions (except NH₃) occurred in November to March and were concentrated in the central cities of Changchun and Harbin and the surrounding cities. Open burning of straw made an important contribution to PM_2.5 in the central regions of the northeastern plain during autumn and spring, while domestic coal combustion for heating purposes was significant with respect to SO₂ and PM_2.5 emissions during autumn and winter. Furthermore, based on Principal Component Analysis and Multivariable Linear Regression model, air temperature, relative humidity, electricity and energy consumption, and the urban and rural population were optimized to be representative indicators for rapidly assessing the magnitude of regional atmospheric pollutants in the HCA. Such indicators and equations were demonstrated to be useful for local atmospheric environment management.     

Spatiotemporal variations of ambient air pollutants and meteorological influences over typical urban agglomerations in China during the COVID-19 lockdown

To investigate the air quality change during the COVID-19 pandemic, we analyzed spatiotemporal variations of six criteria pollutants in nine typical urban agglomerations in China using ground-based data and examined meteorological influences through correlation analysis and backward trajectory analysis under different responses. Concentrations of PM_2.5, PM₁₀, NO₂, SO₂ and CO in urban agglomerations respectively decreased by 18%–45% (30%–62%), 17%–53% (22%–39%), 47%-64% (14%–41%), 9%–34% (0%–53%) and 16%-52% (23%–56%) during Lockdown (Post-lockdown) period relative to Pre-lockdown period. PM_2.5 pollution events occurred during Lockdown in Beijing-Tianjin-Hebe (BTH) and Middle and South Liaoning (MSL), and daily O₃ concentration rose to grade Ⅱ standard in Post-lockdown period. Distinct from the nationwide slump of NO₂ during Lockdown period, a rebound (～40%) in Post-lockdown period was observed in Cheng-Yu (CY), Yangtze River Middle-Reach (YRMR), Yangtze River Delta (YRD) and Pearl River Delta (PRD). With slightly higher wind speed compared with 2019, the reduction of PM_2.5 (51%–62%) in Post-lockdown period is more than 2019 (15%–46%) in HC (Harbin-Changchun), MSL, BTH, CP (Central Plain) and SP (Shandong-Peninsula), suggesting lockdown measures are effective to PM_2.5 alleviation. Although O₃ concentrations generally increased during the lockdown, its increment rate declined compared with 2019 under similar sunlight duration and temperature. Additionally, unlike HC, MSL and BTH, which suffered from additional (> 30%) air masses from surrounding areas after the lockdown, the polluted air masses reaching YRD and PRD mostly originated from the long-distance transport, highlighting the importance of joint regional governance.     

Chemical characteristics, oxidative potential, and sources of PM2.5 in wintertime in Lahore and Peshawar, Pakistan

The chemical characteristics, oxidative potential, and sources of PM_2.5 were analyzed at the urban sites of Lahore and Peshawar, Pakistan in February 2019. Carbonaceous species, water soluble ions, and metal elements were measured to investigate the chemical composition and sources of PM_2.5. The dithiothreitol (DTT) consumption rate was measured to evaluate the oxidative potential of PM_2.5. Both cities showed a high exposure risk of PM_2.5 regarding its oxidative potential (DTT_v). Carbonaceous and some of the elemental species of PM_2.5 correlated well with DTT_v in both Lahore and Peshawar. Besides, the DTT_v of PM_2.5 in Lahore showed significant positive correlation with most of the measured water soluble ions, however, ions were DTT-inactive in Peshawar. Due to the higher proportions of carbonaceous species and metal elements, Peshawar showed higher mass-normalized DTT activity of PM_2.5 compared to Lahore although the average PM_2.5 concentration in Peshawar was lower. The high concentrations of toxic metals also posed serious non-carcinogenic and carcinogenic risks to the residents of both cities. Principle component analysis coupled with multiple linear regression was applied to investigate different source contributions to PM_2.5 and its oxidative potential. Mixed sources of traffic and road dust resuspension and coal combustion, direct vehicle emission, and biomass burning and formation of secondary aerosol were identified as the major sources of PM_2.5 in both cities. The findings of this study provide important data for evaluation of the potential health risks of PM_2.5 and for formulation of efficient control strategies in major cities of Pakistan.     

油田井口加热炉烟尘排放超标原因分析及治理方法

针对井口加热炉燃用套管气出现的烟尘排放超标问题,从燃烧方式及燃料组成方面分析发现,加热炉所采用的扩散式燃烧,火焰面燃料侧缺少氧气,燃料产生热分解生成炭黑颗粒;另外,套管气含有大量的重碳烷烃,其稳定性差、分解温度低,加剧了热分解反应。因此,控制套管气质量和改变燃烧方式是治理烟尘排放超标的基本途径。但是井口加装轻烃回收装置,分离出套管气中的重碳烷烃,成本高不可行。最终,基于预混燃烧理论,设计了双调风预混燃烧装置,现场实施结果表明,不仅烟尘排放降低了87.8%,而且NOx排放降低了58.6%、热效率提升了8.2%。实践证明,预混燃烧是治理井口加热炉烟尘排放超标的有效方法。     

Species diversity and leaf functional traits of understory vegetation one year after severe burning北大核心CSCD

以北京油松(Pinus tabuliformis)人工林为研究对象,采用独立样本T检验、冗余分析等方法,分析重度火烧1年后林下植被(灌木层和草本层)的物种多样性、叶功能性状及其与土壤因子的关系.结果显示:(1)与对照样地相比,重度火烧后灌木层物种丰富度指数极显著降低(P <0.01),但Shannon指数、Simpson指数以及Pielou指数虽呈下降趋势但未达显著水平(P> 0.05);草本层除Pielou指数外,各物种多样性指数均显著增加(P <0.05).(2)重度火烧样地灌木层和草本层的叶厚度(LT)、叶干物质含量(LDMC)、叶碳含量(LCC)、叶磷含量(LPC)均高于对照样地,而比叶面积(SLA)、叶氮含量(LNC)、叶片氮磷比(N:P)、叶绿素含量(CHL)低于对照样地,除灌木层LPC和N:P及草本层SLA、LCC和LPC外,其他各叶功能性状在火烧与对照间差异均达显著水平.对于不同生活型而言,对照样地的LDMC、LNC、LCC、CHL存在显著差异,而在重度火烧后差异不显著;LT、SLA在重度火烧和对照样地上均呈现显著差异;而LPC、N:P在重度火烧与对照样地上均无显著差异.(3)重度火烧后1年,灌木层和草本层的叶功能性状均仅与土壤含水率、容重和非毛管孔隙度密切相关.本研究表明在油松人工林重度火烧后1年,灌木层物种多样性降低,而草本层物种多样性增加,灌草层的各叶功能性状主要受土壤物理性质的影响呈现不同的变化规律.(图4参45)     

滇池外海北岸封闭水域控养水葫芦对水质的影响

在滇池外海北岸污染严重的0.25 km2封闭性蓝藻治理试验示范区内控养水葫芦,以削减富营养化水体内源氮(N)、磷(P)等污染物,探讨有效改善湖泊水质的生物治理措施.6月底按9.30 kg m-2投放水葫芦种苗,控养面积2.51hm2,示范区水面覆盖度为10%.结果显示:水葫芦放养后生长迅速,特别是在7-9月份,最大生长速率达37 2.7 g m-2 d-1;整个植株干物质平均N、P含量分别为23.22 g kg-1和5.03 g kg-1,每t鲜重水葫芦吸收1.63 kg N、0.35 kg P,通过水葫芦种养示范工程,直接由示范工程水域吸收带走N 1.15 t、P 0.25 t;水葫芦生长期间(7-12月),种养区较对照区水体DO、SD和p H均有下降;水葫芦根系具有较好的吸附拦截浮游藻类效果,致使种养区水体TN、TP和CODMn浓度显著高于对照区(P<0.05),并与水体Chl-a浓度显著正相关(P<0.05);水葫芦采收后并未引起二次污染,水质无恶化趋势.综上认为,规模化控养水葫芦可显著削减水体N、P等内源污染负荷,同时对浮游藻类吸附拦截效果明显,可将其滞留于特定水域,又能吸收利用藻类衰亡释放到水体的污染物,减轻外部空白水域水质恶化的压力.     

Evidence for the involvement of Fe(IV) in water treatment by Fe(III)-activated sulfite

Water contamination by emerging organic pollutants is calling for advanced methods of remediation such as iron-activated sulfite-based advanced oxidation. Sulfate radical, SO₄^??, and hydroxyl radical, ^?OH, are the primary reactive intermediates formed in the Fe(III)/sulfite system, yet the possible involvement of Fe(IV) produced from Fe(II) and persulfates is unclear. Here we explored the role of Fe(IV) in the Fe(III)/sulfite system by methyl phenyl sulfoxide (PMSO) probe assay, electron paramagnetic resonance spectra analysis, alcohol scavenging experiment, and kinetic simulation. Results show that PMSO is partially transformed into methyl phenyl sulfone (PMSO₂), thus evidencing Fe(IV) formation. The remaining degradation of PMSO is due to SO₄^?? and ^?OH. The contribution of Fe(IV) versus free radicals is progressively promoted when the Fe(III)-sulfite reaction proceeds, with an upper limit of 80–90%. The contribution of Fe(IV) versus free radicals increases with Fe(III) and sulfite dosages, and decreases with increasing pH. Overall, our findings demonstrate the involvement of Fe(IV) in the Fe-catalyzed sulfite auto-oxidation process.

     

Environmental risks and the potential benefits of nanopesticides: a review

Environmental Chemistry Letters - With the escalating food demand of the ever-increasing global population and the rapid development of nanotechnology, nanopesticides are being proposed as...     

Product identification and toxicity change during oxidation of methotrexate by ferrate and permanganate in water

• Oxidation of methotrexate by high-valent metal-oxo species was first explored. • Fe(VI) presented a higher reactivity to MTX than Mn(VII) at pH 8.0. • Ketonization and cleavage of peptide bond were two initial reaction pathways. • Products of MTX were not genotoxic, neurotoxic, or endocrine-disrupting chemicals. • The less biodegradable products exhibited developmental and acute/chronic toxicity. Accompanying an annual increase in cancer incidence, the global use of anticancer drugs has remarkably increased with their worldwide environmental prevalence and ecological risks. In this study, the oxidation of methotrexate (MTX), a typical anticancer drug with ubiquitous occurrence and multi-endpoint toxicity, by ferrate(VI) (Fe(VI)) and permanganate (Mn(VII))) was investigated in water. Fe(VI) exhibited a higher reactivity with MTX (93.34 M⁻¹ s⁻¹) than Mn(VII) (3.01 M⁻¹ s⁻¹) at pH 8.0. The introduction of Cu(II) and Fe(III) at 1.0 mM improved the removal efficiency of 5.0 μM MTX by 100.0 μM Fe(VI) from 80% to 95% and 100% after 4 min, respectively. Seven oxidized products (OPs) were identified during oxidative treatments, while OP-191 and OP-205 were characterized as specific products for Fe(VI) oxidation. Initial ketonization of the L-glutamic acid moiety and cleavage of the peptide bond of MTX were proposed. Additionally, a multi-endpoint toxicity evaluation indicated no genotoxicity, neurotoxicity, or endocrine-disrupting effects of MTX and its OPs. Particularly, serious developmental toxicity in zebrafish larvae was observed in the treated MTX solutions. Based on the acute and chronic aquatic toxicity prediction, OP-190, OP-192, OP-206, and OP-208 were deemed toxic or very toxic compared to harmful MTX. Furthermore, the reduced biodegradability index from 0.15 (MTX) to −0.5 to −0.2 (OP-192, OP-206, and OP-468) indicated the formation of lower biodegradable OPs. Overall, this study suggests that Fe(VI) and Mn(VII) oxidation are promising treatments for remediating anticancer drug-contaminated water. However, the environmental risks associated with these treatments should be considered in the evaluation of water safety.