Formic acid and acetic acid measurements during the Southern California Air Quality Study

As part of the Southern California Air Quality Study (SCAQS), ambient levels of gas phase formic acid and acetic acid have been measured at four locations: a ‘control’ site (San Nicholas Island), a source-dominated coastal site (Long Beach) and two inland smog receptor sites (Claremont and Palm Springs). Samples were collected on alkaline traps and were analyzed by size exclusion liquid chromatography with ultraviolet detection. Levels of gas phase formic acid (up to 19 ppb) and acetic acid (up to 17 ppb) exhibited diurnal (frequent night-time maxima), spatial and seasonal variations. During summer smog episodes, concentrations increased from 0.6 ppb at the ‘control’ site to up to 13–19 ppb at the inland smog receptor sites reflecting primary emissions and in situ formation during transport inland. The acetic acid/formic acid (A/F) ratio decreased from coastal to inland sites. At the coastal site levels of both acids and the A/F ratio were substantially higher during the fall than during the summer.     

Formic acid and acetic acid in the western Sierra Nevada,California

This paper reports the results of measurements of formic and acetic acid at four sites located along the western slope of the Sierra Nevada and compares the results with those of earlier studies. Formic acid concentrations ranged from approximately 1 to 40 ppb; those of acetic acid ranged from approximately 0.5 to 13 ppb. Mean formic acid concentrations were 18 ppb at Tehachapi, located at the southern extremity of the range, and between 12 and 13 ppb at the three other sites. Mean acetic acid concentrations ranged from 3.9 ppb at Blodgett Experimental Forest, located at the northern extremity, to 8.0 ppb at Yosemite. Comparison with previous studies indicates that carboxylic acid levels measured in the Sierra Nevada are higher than those measured in past studies, and in many cases average concentrations of both formic and acetic acids observed during this study were greater than the previously reported maxima. Comparisons were also made to nitric acid concentrations measured at Yosemite and Giant Forest from October 1986 to September 1987. At Yosemite, annual nitric acid concentrations averaged 0.20 ppb during the day, and 0.06 ppb at night; and at Giant Forest, nitric acid averaged 0.17 ppb during the day, and 0.05 ppb at night. Thus, the high formic and acetic acid concentrations observed in this study suggest that carboxylic acid are major contributors to the overall flux of ambient acid deposition in the western Sierra Nevada.     

贵阳市区大气降水中甲酸和甲醛含量的季节变化特征

采用离子色谱法测定了贵阳市区大气降水中甲酸和甲醛含量并分析了其浓度的变化规律及其来源.结果表明,两者的年体积平均浓度(volume mean weight average, VMWA)分别为(13.27±25.92)μmol/L和(7.89±8.92) μmol/L,并且夏半年甲醛和甲酸浓度低于冬半年的浓度,这可能与该地区冬季干燥少雨、降雨的同时易伴随干沉降有关.甲醛和甲酸的昼夜变化(白天>夜晚)则反映了人为活动和大气光化学反应对其浓度的影响.相关性分析发现,甲醛和甲酸是在云下(below-cloud)过程进入大气降水的,随降雨的进行,雨水中甲酸和甲醛浓度逐渐减小,降雨起到稀释作用.同时,雨水中甲酸和甲醛存在显著相关关系(r=0.68, P<0.001)说明两者存在类似的来源或反应.甲醛液相氧化反应生成的甲酸不能很好地解释所检测到甲酸数据,说明甲醛氧化反应不是贵阳地区甲酸的主要来源,植物或人类活动产生的不饱和碳氢化合物的氧化可能是甲醛和甲酸的主要来源.     

共沸-分馏连续操作处理醇酮装置酸性废水

为了降低环己醇、环己酮生产装置产生的含甲酸废水的COD,使其达到排放标准,降低废水排放量,减少环境污染的目的,根据共沸-分馏间歇操作处理醇酮装置酸性废水研究获得的工艺参数,采用共沸-分馏连续操作处理该酸性废水,并从中回收甲酸。介绍了共沸-分馏连续操作处理醇酮装置酸性废水的工艺过程、操作方法,给出了共沸-分馏连续操作处理该废水并回收甲酸的实验数据,完成了间歇操作改连续操作过程的工艺研究,研究结论为进一步工业化生产装置设计奠定了基础。通过研究得出,采用共沸-分馏连续操作处理该酸性废水,废水的COD由1.6×105mg/L降至3.0×102mg/L以下,达此标准水为80%以上,废水的COD去除率达到99%以上,甲酸回收率80%,连续操作实验结果优于间歇操作。     

Potential of capillary electrophoresis mass spectrometry for the characterization and monitoring of amine-derivatized naphthenic acids from oil sands process-affected water

Capillary electrophoresis coupled to mass spectrometry(CE–MS) was used for the analysis of naphthenic acid fraction compounds(NAFCs) of oil sands process-affected water(OSPW). A standard mixture of amine-derivatized naphthenic acids is injected directly onto the CE column and analyzed by CE–MS in less than 15 min. Time of flight MS analysis(TOFMS), optimized for high molecular weight ions, showed NAFCs between 250 and 800 m/z. With a quadrupole mass analyzer, only low-molecular weight NAFCs(between 100 and 450 m/z) are visible under our experimental conditions. Derivatization of NAFCs consisted of two-step amidation reactions mediated by 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide(EDC), or mediated by a mixture of EDC and N-hydroxysuccinimide, in dimethyl sulfoxide, dichloromethane or ethyl acetate. The optimum background electrolyte composition was determined to be 30%(V/V) methanol in water and 2%(V/V) formic acid. NAFCs extracted from OSPW in the Athabasca oil sands region were used to demonstrate the feasibility of CE–MS for the analysis of NAFCs in environmental samples, showing that the labeled naphthenic acids are in the mass range of 350 to 1500 m/z.     

Formic acid as an alternative reducing agent for the catalytic nitrate reduction in aqueous media

Formic acid was used for the nitrate reduction as a reductant in the presence of Pd:Cu/γ-alumina catalysts. The surface characteristics of the bimetallic catalyst synthesized by wet impregnation were investigated by SEM, TEM-EDS. The metals were not distributed homogeneously on the surface of catalyst, although the total contents of both metals in particles agreed well with the theoretical values. Formic acid decomposition on the catalyst surface, its influence on solution pH and nitrate removal efficacy was investigated. The best removal of nitrate (50 ppm) was obtained under the condition of 0.75 g/L catalyst with Pd:Cu ratio (4:1) and two fold excess of formic acid. Formic acid decay patterns resembled those of nitrate removal, showing a linear relationship between kf (formic acid decay) and k (nitrate removal). Negligible amount of ammonia was detected, and no nitrite was detected, possibly due to buffering effect of bicarbonate that is in situ produced by the decomposition of formic acid, and due to the sustained release of H2 gas.     

Atmospheric gaseous organic acids in winter in a rural site of the North China Plain

Organic acids are important contributors to the acidity of atmospheric precipitation,but their existence in the Chinese atmosphere is largely unclear.In this study,twelve atmospheric gaseous organic acids,including C₁-C₉ alkanoic acids,methacrylic acid,pyruvic acid,and benzoic acid,were observed in the suburb of Wangdu,Hebei Province,a typical rural site in the northern China plain from 16^th December,2018 to 22^nd January,2019,using a Vocus@Proton-Trans...     

模拟三峡库区消落带优势植物根系低分子量有机酸对土壤中铅的解吸动力学

三峡库区消落带落干期时会生长大量植被,其根系分泌的低分子量有机酸会对消落带土壤中重金属的活化带来一定影响,为此,本研究通过水培法以及利用去离子水直接浸提其根际土测出三峡库区优势植物狗牙根和稗草根系分泌的低分子量有机酸种类和含量,并模拟优势植物所分泌的单一有机酸和混合有机酸分别对消落带土壤中的铅(Pb)进行解吸,探究其对消落带土壤中铅的解吸动力学.结果表明,狗牙根根系分泌的低分子量有机酸种类和含量均大于稗草,其中柠檬酸、丙二酸、乙酸、苹果酸是两种植株根系均分泌的有机酸,且乙酸含量最高,分别为0.765 mmol·kg-1、0.261 mmol·kg-1,而在狗牙根和稗草根际土中均检测到柠檬酸、丙二酸、乙酸;选取柠檬酸、丙二酸、乙酸对消落带土壤中铅进行解吸时,发现当有机酸浓度≤1 mmol·L~(-1)时,有机酸解吸量由高到低为:丙二酸柠檬酸乙酸;而当有机酸浓度1 mmol·L~(-1)时,有机酸解吸量由高到低为:柠檬酸丙二酸乙酸,且低分子量有机酸在土壤中含量低时,抑制土壤对Pb的解吸;含量高时,促进土壤对Pb的解吸.在解吸过程中,0~240 min为快反应阶段,240 min后为慢反应阶段,准二级动力学方程拟合效果最好.     

深圳大学城园区典型OVOCs污染特征与来源解析

采用质子转移反应质谱仪（PTR-MS）对深圳大学城园区2017年不同季节（分干湿两季）的6种典型OVOCs和其他非甲烷烃类（NMHCs）进行连续在线监测,分析其干湿季的浓度特征与日变化规律,并应用光化学龄的参数化方法开展OVOCs的来源解析.结果表明,在观测的6种OVOCs中,甲醇的平均浓度最高,达10×10^-9~12×10^-9,其次是乙酸、丙酮和乙醛,约2~5×10^-9,甲酸和丁酮的含量最低,仅1×10^-9~2×10^-9.通过日变化观察到的OVOCs湿季峰值浓度时间明显早于干季,乙醛表现出与臭氧（O₃）相似的日变化特征,揭示了其可能存在二次来源;甲醇和丁酮的峰值浓度时间均早于O₃,可能存在重要的一次排放源.采用光化学龄模型解析出日间污染物来源比例：在污染较重的干季,甲醇、乙醛、丙酮和丁酮的人为一次源占主导,甲酸和乙酸的二次源是主要贡献者;在较清洁的湿季,天然源成为乙醛、丙酮、丁酮、甲酸和乙酸的主要来源.     

催化剂Ru/ZrO2-CeO2催化湿式氧化苯酚

催化剂Ru/ZrO₂-CeO₂催化湿式氧化苯酚的过程表明,Ru/ZrO₂-CeO₂可以显著提高COD和苯酚去除效果,当反应温度为170℃,压力为3 MPa,反应120 min后,COD和苯酚的去除率分别达到了99％和100％.试验还考察了不同反应条件对苯酚溶液COD去除的影响,并获得了最优的反应条件：温度为170℃,压力为3 MPa,催化剂的投加量为5　g/Ｌ,搅拌速度为500 r/min.通过对中间产物的分析,本研究提出了催化湿式氧化苯酚的简单路径图,认为苯酚首先被氧化成小分子有机酸,接着小分子有机酸被氧化成二氧化碳和水.前一个过程是快速反应,后一个过程中的乙酸氧化是慢速过程,需要在高温下才能完成.乙酸的氧化主要是自由基攻击α碳上的C—H键,先生成甲酸,并最终生成二氧化碳和水.     

Ti-Ce系列催化剂上乙酸的催化湿式氧化反应

采用Ti-Ce系列湿式氧化催化剂,研究模型反应物乙酸在催化湿式氧化反应中的动力学影响因素以及反应过程产物.结果表明,乙酸的催化湿式氧化受到催化剂用量、反应温度、反应体系酸度以及氧分压的影响较大.当反应温度230℃,氧分压2～2.5MPa,催化剂量5g/L,反应液初始pH3.0时,反应1h后即可使乙酸浓度(以COD计)去除率在90%以上.通过离子色谱,检测了反应过程中的甲酸中间体,结果表明,催化剂的存在不仅加速了湿式氧化反应速率,而且也改变了反应历程.     

Electrochemical oxidation of polyethylene glycol in electroplating solution using paraffin composite copper hexacyanoferrate modified (PCCHM) anode

Electrochemical oxidation of polyethylene glycol (PEG) in an acidic(pH 0.18 to 0.42) and high ionic strength electroplating solution was investigated. The electroplating solution is a major source of wastewater in the printing wiring board industry. A paraffin composite copper hexacyanoferrate modified(PCCHM) electrode was used as the anode and a bare graphite electrode was used as the cathode. The changes in PEG and total organic carbon (TOC) concentrations during the course of the reaction were monitored. The efficiency of the PCCHM anode was compared with bare graphite anode and it was found that the former showed significant electrocatalytic property for PEG and TOC removal. Chlorides present in the solution were found to contribute significantly in the overall organic removal process. Short chain organic compounds like acetic acid, oxalic acid, formic acid and ethylene glycol formed during electrolysis were identified by HPLC method. Anode surface area and applied current density were found to influence the electro-oxidation process, in which the former was found to be dominating. Investigations of the kinetics for the present electrochemical reaction suggested that the two stage first-order kinetic model provides a much better representation of the overall mechanism of the process if compared to the generalized kinetic model.     

In-digester reduction of organic sulfur compounds in kraft pulping

This experimental research examines the relationship between the formation of organic sulfur compounds and delignification during kraft wood pulping. A phase transition point (PTP) was discovered below and above which the formation of total organic sulfur compounds, with respect to delignification, changes significantly. The PTP occurs at approximately pulp kappa number 35 for softwoods and 20 for hardwoods. The PTP is directly related to the phase transition in kraft delignification from bulk to residual delignification. Significant in-digester odor reduction can be achieved using phase transition cooking (PTC), i.e. limiting delignification to the bulk delignification phase or the PTP. It was also discovered that anthraquinone (AQ) as a catalytic additive can reduce organic sulfur compound formation during kraft pulping. The reduction of sulfur compound formation is linearly proportional to the square root of the level of AQ addition (in percent). A 40% in-digester reduction in total reduced sulfur (TRS) formation can be achieved by using PTC and AQ in kraft pulping.     

Formic acid and acetic acid: Emissions,atmospheric formation and dry deposition at two southern California locations

Emission rates, in situ formation rates and removal rates by dry deposition are estimated for formic acid (HCOOH, C1) and acetic acid (CH₃COOH, C2), which are the most abundant acids in southern California air and together account for much of the airborne acidity and are the leading contributors to acid dry deposition. Using data for eight unreactive tracers, direct emission rates during the fall 1987 are estimated to be 5.6 and 12.8 metric tons d⁻¹ for C1 and C2, respectively, at a coastal source-dominated site. These emissions rates increase to 9.6(C1) and 20.4(C2) metric tons d⁻¹ during the summer. In situ formation in the atmosphere via the ozone-olefin reaction is an important source for both acids. This reaction produces an estimated 25.0 and 10.1 metric tons d⁻¹ of C1 and C2, respectively, during the day and 34.5 (C1) and 4.3 (C2) metric tons d⁻¹ at night. More acetic acid than formic acid is emitted by direct sources, with C2/C1 emission rate ratios of 2.1–2.3. The reverse is true of in situ formation, with C1/C2 production rate ratios of 2.5 (day) and 8.0 (night). Dry deposition removal rates depend on season (fall > summer) and location (inland > coastal) and are 22–52 metric tons d⁻¹ for C1, and 32–83 metric tons d⁻¹ for C2. Source (emissions + in situ formation) and sink (dry deposition) terms are of the same magnitude in all six cases studied and balance each other well in three of these cases. Uncertainties in emission, in situ production and removal rates are discussed and reflect uncertaintes in olefin and unreactive tracer emission rates, yields of organic acids from the Criegee biradical (ozone-olefin reaction), and dry deposition velocity, respectively.     

The use of thymol as a biocide in rainwater samples

An essential requirement for any rainwater composition study based on sampling periods longer than that of individual events, is the selection of a biocide which prevents the biological degradation of rainwater organic acids, such as formic and acetic acid. In this report data are presented from a series of tests of biocidal activity of several compounds. Chloroform was confirmed as an effective rainwater biocide which quantitatively preserves formic acid from biological degradation in rainwater. Of the compounds tested, only bromoform and thymol (2-isopropyl-5-methyl phenol) were as effective as chloroform in preventing biological degradation of formic acid in rainwater. However, since bromoform produced an acid on standing, probably hydrobromic acid, it was unsuitable for use as a biocide. Therefore only thymol was found to be suitable as a biocide in rainwater collected in south-eastern Australia. As thymol is a solid, and hence non-volatile, it offers some advantage over the traditional use of chloroform.     

低分子有机酸对硫杆菌活性的抑制作用及对土壤重金属脱除的影响

施用有机肥能够降低污染土壤重金属溶解性和生物可利用性,但在淹水厌氧等环境中,有机肥会分解产生大量低分子有机酸,会抑制嗜酸性硫杆菌的生物活性.通过摇瓶实验研究了低分子有机酸对硫杆菌的毒害抑制效果和不同硫杆菌对各类有机酸的耐受水平.结果表明,纯体系培养下,A.ferrooxidans和A.thiooxidans活性抑制率在72 h内达到90%以上,所需甲、乙、丙、丁酸最低浓度分别为41.2、78.3、43.2、123.4 mg·L~(-1)和81.9、230.4、170.1、123.4 mg·L~(-1).其中,甲酸对A.ferrooxidans和A.thiooxidans的抑制作用最显著,A.thiooxidans相比A.ferrooxidans对4种有机酸具有更高的耐受性.新鲜重金属污染土壤在生物酸化初期(0 h)加入4种有机酸对后续土壤酸化过程影响较小,但12 h后加入有机酸却能使土壤生物酸化基本停止,导致土壤重金属脱除率大幅度下降.这为有机肥改良重金属污染土壤的生物修复可行性提供一定理论依据.     

低分子量有机酸提取土壤中部分重金属的拟合模型研究

为研究不同浓度低分子量有机酸与提取的土壤重金属含量之间的关系,本文以采自安徽省安庆市某铜矿区及其周围的土壤为例,通过浸提法,研究了不同浓度苹果酸、甲酸对采样点土壤中重金属Cu、Mn、Zn、Pb提取能力的影响并进行模型拟合.结果表明:不同浓度苹果酸和甲酸对采样点土壤中重金属的提取量不同,两种有机酸对低pH、高重金属含量采样点及其周围土壤中的重金属提取量较大,两种低分子量有机酸对S6采样点的重金属Mn的提取量最大,分别为322.5 mg·kg~(-1)和193.58 mg·kg~(-1),提取率达70.02%和42.03%,Zn、Pb次之,Cu最低;随着苹果酸、甲酸浓度的升高,土壤中重金属Cu、Mn、Zn、Pb的提取量增加,苹果酸对土壤中重金属的提取能力大于甲酸;拟合模型对于两种低分子量有机酸与其提取的土壤中部分重金属含量之间的关系,具有较好的拟合性,其决定系数R~2在0.8293～0.9990之间,都具有显著性(p0.05),该模型可以定量表征低分子量有机酸对土壤重金属的提取能力,此研究结果为土壤中重金属的固定化和增强植物修复受重金属污染的土壤提供了理论支持.     

Ⅰ Ⅱ-ASBR中厌氧颗粒污泥的微生物组成及特性

在35℃下以奶粉人工合成废水为底物连续运行了两段厌氧反应器(ⅠⅡ-ASBR),且于ⅠⅡ两柱中形成了两种不同的厌氧颗粒污泥,为了解厌氧颗粒污泥的微生态结构及生物学特性,对ⅠⅡ两柱中厌氧颗粒污泥的形态及微生物组成进行扫描电镜观察,并测定了其不同基质中的比产甲烷活性、辅酶F420和胞外多聚物的含量。结果表明:ⅠⅡ-ASBR反应器ⅠⅡ两柱中厌氧颗粒污泥形态及微生物组成差异明显,Ⅰ柱的厌氧颗粒污泥大而密实,Ⅱ柱的较小,呈多孔的网状结构,Ⅰ柱中厌氧颗粒污泥以甲烷八叠球菌、球菌及短杆菌为主,丝状菌较少,Ⅱ柱则以丝状菌、短杆菌为主,球菌较少;Ⅰ柱颗粒污泥利用葡萄糖、甲酸、丙酸的产甲烷活性较高,利用乙酸的活性相对较低,Ⅱ柱颗粒污泥利用葡萄糖、乙酸的产甲烷活性较高,而利用甲酸、丙酸的产甲烷活性较低;辅酶F420的含量Ⅱ柱比Ⅰ柱明显要高,而胞外多聚物含量Ⅰ柱比Ⅱ柱的高。     

膜分离技术治理糠醛废水

糠醛生产废水中含1—2.5％的乙酸,若废水外排,会造成大量损失且污染环境.通过30—80对膜组装的400×800mm电渗析器中试操作,回收了浓度为20％的乙酸,再经萃取、精馏工艺得到工业一级乙酸.治理后的废水含酸量为0.02—0.05％,可安全排放及回用.中试技术指标优于小试,重现良好.     

Catalytic wet air oxidation of phenol with functionalized carbon materials as catalysts：Reaction mechanism and pathway

The development of highly active carbon material catalysts in catalytic wet air oxidation（CWAO）has attracted a great deal of attention. In this study different carbon material catalysts（multi-walled carbon nanotubes,carbon fibers and graphite） were developed to enhance the CWAO of phenol in aqueous solution. The functionalized carbon materials exhibited excellent catalytic activity in the CWAO of phenol. After 60 min reaction,the removal of phenol was nearly100% over the functionalized multi-walled carbon,while it was only 14% over the purified multi-walled carbon under the same reaction conditions. Carboxylic acid groups introduced on the surface of the functionalized carbon materials play an important role in the catalytic activity in CWAO. They can promote the production of free radicals,which act as strong oxidants in CWAO. Based on the analysis of the intermediates produced in the CWAO reactions,a new reaction pathway for the CWAO of phenol was proposed in this study. There are some differences between the proposed reaction pathway and that reported in the literature. First,maleic acid is transformed directly into malonic acid. Second,acetic acid is oxidized into an unknown intermediate,which is then oxidized into CO2 and H2O. Finally,formic acid and oxalic acid can mutually interconvert when conditions are favorable.