夏秋季节焦化厂附近大气中臭氧及其前体物变化特征和臭氧生成潜势分析

2012年6—10月,在我国北方某焦化厂厂界附近开展了O3、NO x、CO体积分数在线监测及VOCs样品采集分析工作,获得了夏、秋两季焦化厂厂界O3及其前体物的体积分数及其日变化趋势。焦化厂厂界附近O3、NO、CO体积分数均呈单峰型日变化,O3体积分数的季节差异不明显,夏季仅略高于秋季,而NO、CO体积分数秋季高于夏季,作为二次反应产物的NO2,其变化幅度秋季比夏季强烈。夏季TVOCs在各监测时段的小时体积分数呈现先上升后下降的日变化趋势,而秋季则呈现逐渐下降的日变化趋势。由较小VOCs/NO x的比值可初步判断,该焦化厂所在区域的大气光化学臭氧生成潜势处于VOCs控制区。在焦化厂下风向厂界附近,夏、秋两季TVOCs平均体积分数分别为(43.8±45.0)×10-9和(26.7±29.6)×10-9,苯系物、烷烃、烯烃的平均体积分数分别为(34.3±28.1)×10-9和(14.4±14.8)×10-9、(5.3±11.8)×10-9和(7.0±7.7)×10-9、(4.3±5.0)×10-9和(5.3±7.1)×10-9。夏、秋两季焦化厂附近臭氧生成潜势贡献最大的是苯系物(47.6%~65.8%),其次是烯烃(28.0%~41.9%),再次是烷烃(6.3%~10.5%)。     

宝鸡市大气PM_(10)中水溶性物质的组成及特征研究

2008年冬、春季在宝鸡市4个不同功能区采集PM10样品,探讨了PM10中水溶性物质的化学组成、时空分布特征以及来源。结果表明,冬、春季PM10的平均质量浓度分别为(402±100)、(410±160)μg/m3,无明显季节差异,冬季以交通干道区的PM10浓度为最高,而春季则以商贸区的PM10浓度为最高;冬、春季PM10中水溶性有机碳(WSOC)浓度最高值均出现在商贸区,最低值则分别出现在背景点和交通干道区,水溶性无机碳(WSIC)浓度最高值分别出现在交通干道区和商贸区,最低值均出现在背景点;冬、春季PM10中所含大多数无机离子浓度不存在显著空间差异,但不同功能区PM10中无机离子所占质量分数差异较明显;冬、春季PM10中的水溶性物质质量浓度分别为207、151μg/m3,在PM10中所占质量分数分别为51%和40%,其中,冬、春季水溶性物质浓度最高的分别为居民区和商贸区;冬季PM10中WSOC浓度与SO24-、NO3-浓度有较好的相关性,说明冬季PM10中WSOC的主要组分为二次有机气溶胶,而春季PM10中WSOC浓度与SO42-、NO3-浓度的相关性相对较差,这是由于一次有机气溶胶对WSOC的贡献率较冬季显著增大;宝鸡市与北京市大气PM10浓度、PM10中的SO42-、NO3-、NH4+浓度最为接近;广州市大气PM10中的SO42-所占质量分数(14%)要高于北方城市(宝鸡市和北京市均为9%)。     

天津市秋季臭氧浓度影响因素及相关关系研究

选择天津市秋季典型重污染时期2005年11月2～7日近地面大气O3、NO、NO2、CO、紫外线(UV)强度和温度等观测数据,研究O3浓度的时间变化特征及其与相关前体物、气象条件的相关关系.结果表明,在观测期间O3浓度存在明显的日变化周期,在13:00～14:00时浓度最大,夜间变化平缓;O3浓度与NO、NO2、NOx和CO等前体物呈较好的负相关关系;温度和UV与O3浓度密切相关,昼间O3与UV呈相同变化趋势,相关系数达0.71,O3浓度变化滞后于UV变化,将O3浓度与前1小时的UV对比分析,相关系数提高到0.81.     

重庆市核心区黑碳气溶胶浓度特征以及影响因素分析

2013年4月至2014年2月期间利用重庆市大气超级站的黑碳气溶胶(black carbon,BC)、气态污染物(SO2、NOx和O3)和颗粒物观测数据,分析了重庆市BC浓度的变化特征及与能见度、颗粒物以及SO2、NOx和O3气态污染物的相关性。观测期间BC年日均值为(4.86±2.37)μg/m3,浓度范围为1.32~11.54μg/m3。秋冬季BC日均浓度及相对偏差比春夏季高。BC和能见度呈负相关性。4个季度的BC与PM10、PM2.5和PM1日均值显著正相关,相关系数最小在夏季,最大在秋季。BC与O3日均值呈负相关性。BC与SO2,NOx日均值显著正相关,表明重庆市BC与SO2,NOx来源相近,即为燃煤和机动车尾气排放。     

南京北郊春季地面臭氧与氮氧化物浓度特征

2009年3—5月,采用NO-NO2-NH3分析仪和O3分析仪对南京市北郊大气O3、NO、NO2和NOx浓度进行连续观测,研究南京北郊春季大气臭氧与氮氧化物浓度变化特征。结果表明:O3浓度的日变化呈单峰型结构,白天较高,夜晚较低,在06:00左右出现最低值,14:00左右出现峰值,且工作日的O3浓度值明显高于周末的O3浓度值。NOx的日变化呈现双峰型变化规律,早上07:00左右出现第1个峰值,下午14:00—15:00左右达到最低值,午夜23:00左右出现第2个峰值。从3—5月份,NO浓度明显下降,3月份的变化幅度比较大;NO2浓度则明显上升,5月份变化幅度较大。3—5月NO与O3之间呈显著的负相关关系,4—5月NO2、NOx与O3呈显著的负相关关系。     

钙基固硫剂对污泥和煤燃烧过程中SO2和NOx释放的影响

在O2气氛下,研究了煤与污泥2种燃料中添加4种钙基固硫剂( CaO、Ca(OH)2、CaCO3和白云石(CaCO3·MgCO3))后的SO2和NOx的释放特性.结果表明:(1)煤燃烧时SO2的释放曲线和NO较相似,呈现2个析出峰;污泥燃烧过程中SO2和NO的释放规律一致,35 s时烟气中SO2和NO瞬时质量浓度达到峰值...     

电化学法去除SO2/NOX的研究进展

本文对采用电化学方法去除SO2/NOx废气这一新的研究方法进行了综述.在用酞花青钴(CoPc)修饰的碳气体扩散电极上,SO2在空气中的体积百分数在20%以下时可以完全被氧化为硫酸,以连二硫酸盐(S2O2-4)作还原剂,Fe2+-EDTA作络合剂时,NO以90%以上的程度还原为NH+4与NH2(SO3H)等低价含氮化合物,产物中未见N2、N2O与NO2等气体,氧化产物SO2-3(或HSO-3)在Pb阴极上还原再生为S2O2-4.用Ce4+作氧化剂可将SO2/NO2氧化为相应的酸,还原产物Ce3+经电解氧化后循环使用.     

电化学法去除SO2/NOX的研究进展

本文对采用电化学方法去除SO2/NOx废气这一新的研究方法进行了综述.在用酞花青钴(CoPc)修饰的碳气体扩散电极上,SO2在空气中的体积百分数在20%以下时可以完全被氧化为硫酸,以连二硫酸盐(S2O2-4)作还原剂,Fe2+-EDTA作络合剂时,NO以90%以上的程度还原为NH+4与NH2(SO3H)等低价含氮化合物,产物中未见N2、N2O与NO2等气体,氧化产物SO2-3(或HSO-3)在Pb阴极上还原再生为S2O2-4.用Ce4+作氧化剂可将SO2/NO2氧化为相应的酸,还原产物Ce3+经电解氧化后循环使用.     

一次光化学污染过程中O_3和NOx的垂直梯度观测研究

为了研究2008年北京奥运会前期污染物浓度变化特征,对北京气象塔3层高度上的大气污染物(NO2和O3)进行加强观测,分析其变化特征。观测结果表明,由于北京奥运会前期采取了严格的空气质量控制措施,NO2浓度相对车辆限行前下降了45.3%,且随着高度递增逐渐降低;O3浓度最大值和日均值有所降低,其最大值出现时间较10年前提前了1~2 h,且有4 h左右处于相对平稳状态。O3浓度峰值主要是受NO2的控制,O3浓度峰值出现时间提前反映出北京大气氧化效率不断提高。对于观测期间出现光化学污染事件,利用同期气象资料和大气污染监测数据分析,发现造成这次大气污染的主要原因是气象因子:地面多处于弱高压场控制中,大气层结稳定,风力较弱(小于2 m/s),并伴随着连续高温、强辐射和低湿。     

一次光化学污染过程中O3和NOx的垂直梯度观测研究

为了研究2008年北京奥运会前期污染物浓度变化特征,对北京气象塔3层高度上的大气污染物（NO2和O3）进行加强观测,分析其变化特征。观测结果表明,由于北京奥运会前期采取了严格的空气质量控制措施,NO2浓度相对车辆限行前下降了45.3%,且随着高度递增逐渐降低;O3浓度最大值和日均值有所降低,其最大值出现时间较10年前提前了12 h,且有4 h左右处于相对平稳状态。O3浓度峰值主要是受NO2的控制,O3浓度峰值出现时间提前反映出北京大气氧化效率不断提高。对于观测期间出现光化学污染事件,利用同期气象资料和大气污染监测数据分析,发现造成这次大气污染的主要原因是气象因子：地面多处于弱高压场控制中,大气层结稳定,风力较弱（小于2 m/s）,并伴随着连续高温、强辐射和低湿。     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

Radionuclides in pinon pine (Pinus edulis) nuts from los alamos national laboratory lands and the dose from consumption

Abstract

One of the dominant tree species growing within and around the eastern portion of Los Alamos National Laboratory (LANL), Los Alamos, NM, lands is the pinon pine (Pinus edulis). Pinon pine is used for firewood, fence posts, and building materials and is a source of nuts for food—the seeds are consumed by a wide variety of animals and are also gathered by people in the area and eaten raw or roasted. This study investigated the (1) concentration of ³H, ¹³⁷Cs, ⁹⁰Sr, ^totU, ²³⁸Pu, ^{239, 240}Pu, and²⁴¹ Am in soils (0‐ to 12‐in. [31 cm] depth underneath the tree), pinon pine shoots (PPS), and pinon pine nuts (PPN) collected from LANL lands and regional background (BG) locations, (2) committed effective dose equivalent (CEDE) from the ingestion of nuts, and (3) soil to PPS to PPN concentration ratios (CRs). Most radionuclides, with the exception of ³H in soils, were not significantly higher (p < 0.10) in soils, PPS, and PPN collected from LANL as compared to BG locations, and concentrations of most radionuclides in PPN from LANL have decreased over time. The maximum net CEDE (the CEDE plus two sigma minus BG) at the most conservative ingestion rate (10 lb [4.5 kg]) was 0.0018 mrem (0.018 μSv); this is far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem (1000 μSv). Soil‐to‐nut CRs for most radionuclides were within the range of default values in the literature for common fruits and vegetables.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.     

Biochemical interaction of six op delayed neurotoxicants with several neurotargets

Abstract

Five organophosphorous insecticides: Leptophos, EPN, Cyano‐fenphos, trichloronate and salithion proved to cause irreversible ataxia not only to chicken but also to mice and sheep. TOCP was included as a reference. Cyanofenphos blocked the catecholamine B‐receptor binding activity with ³H‐norepinephrine at a level similar to that of the specific inhibitor propranolol in the mouse heart preparation. In the lamb heart preparation, the B‐receptor was more sensitive to Leptophos, salithion and TOCP than to propranolol. The six compounds and their oxons were screened for their in‐vitro inhibition to monamine oxidase (MAO), acetyl cholinesterase (AChE) and neurotoxic esterase (NTE) in the brain of either mouse, lamb or chicken. It is believed that their AChE inhibition stands for their acute toxicity, while NTE inhibition is responsible for their paralytic ataxia.     

Phytoextraction of lead-contaminated soil using vetivergrass (<Emphasis Type="Italic">Vetiveria zizanioides</Emphasis> L.), cogongrass (<Emphasis Type="Italic">Imperata cylindrica</Emphasis> L.) and carabaograss (<Emphasis Type="Italic">Paspalum conjugatum</Emphasis> L.)

Background, Aims and Scope The global problem concerning contamination of the environment as a consequence of human activities is increasing. Most of the environmental contaminants are chemical by-products and heavy metals such as lead (Pb). Lead released into the environment makes its way into the air, soil and water. Lead contributes to a variety of health effects such as decline in mental, cognitive and physical health of the individual. An alternative way of reducing Pb concentration from the soil is through phytoremediation. Phytoremediation is an alternative method that uses plants to clean up a contaminated area. The objectives of this study were: (1) to determine the survival rate and vegetative characteristics of three grass species such as vetivergrass, cogongrass and carabaograss grown in soils with different Pb levels; and (2) to determine and compare the ability of the three grass species as potential phytoremediators in terms of Pb accumulation by plants. Methods The three test plants: vetivergrass (Vetiveria zizanioides L.); cogongrass (Imperata cylindrica L.); and carabaograss (Paspalum conjugatum L.) were grown in individual plastic bags containing soils with 75 mg kg⁻¹ (37.5 kg ha⁻¹) and 150 mg kg⁻¹ (75 kg ha⁻¹) of Pb, respectively. The Pb contents of the test plants and the soil were analyzed before and after experimental treatments using an atomic absorption spectrophotometer. This study was laid out following a 3 × 2 factorial experiment in a completely randomized design. Results On the vegetative characteristics of the test plants, vetivergrass registered the highest whole plant dry matter weight (33.85–39.39 Mg ha⁻¹). Carabaograss had the lowest herbage mass production of 4.12 Mg ha⁻¹ and 5.72 Mg ha⁻¹ from soils added with 75 and 150 mg Pb kg⁻¹, respectively. Vetivergrass also had the highest percent plant survival which meant it best tolerated the Pb contamination in soils. Vetivergrass registered the highest rate of Pb absorption (10.16 ± 2.81 mg kg⁻¹). This was followed by cogongrass (2.34 ± 0.52 mg kg⁻¹) and carabaograss with a mean Pb level of 0.49 ± 0.56 mg kg⁻¹. Levels of Pb among the three grasses (shoots + roots) did not vary significantly with the amount of Pb added (75 and 150 mg kg⁻¹) to the soil. Discussion Vetivergrass yielded the highest biomass; it also has the greatest amount of Pb absorbed (roots + shoots). This can be attributed to the highly extensive root system of vetivergrass with the presence of an enormous amount of root hairs. Extensive root system denotes more contact to nutrients in soils, therefore more likelihood of nutrient absorption and Pb uptake. The efficiency of plants as phytoremediators could be correlated with the plants’ total biomass. This implies that the higher the biomass, the greater the Pb uptake. Plants characteristically exhibit remarkable capacity to absorb what they need and exclude what they do not need. Some plants utilize exclusion mechanisms, where there is a reduced uptake by the roots or a restricted transport of the metals from root to shoots. Combination of high metal accumulation and high biomass production results in the most metal removal from the soil. Conclusions The present study indicated that vetivergrass possessed many beneficial characteristics to uptake Pb from contaminated soil. It was the most tolerant and could grow in soil contaminated with high Pb concentration. Cogongrass and carabaograss are also potential phytoremediators since they can absorb small amount of Pb in soils, although cogongrass is more tolerant to Pb-contaminated soil compared with carabaograss. The important implication of our findings is that vetivergrass can be used for phytoextraction on sites contaminated with high levels of heavy metals; particularly Pb. Recommendations and Perspectives High levels of Pb in localized areas are still a concern especially in urban areas with high levels of traffic, near Pb smelters, battery plants, or industrial facilities that burn fuel ending up in water and soils. The grasses used in the study, and particularly vetivergrass, can be used to phytoremediate urban soil with various contaminations by planting these grasses in lawns and public parks. ESS-Submission Editor: Dr. Willie Peijnenburg (wjgm.peijnenburg@rivm.nl)