Optimization of the O3/H2O2 process with response surface methodology for pretreatment of mother liquor of gas field wastewater

• Real ML-GFW with high salinity and high organics was degraded by O₃/H₂O₂ process. • Successful optimization of operation conditions was attained using RSM based on CCD. • Single-factor experiments in advance ensured optimal experimental conditions. • The satisfactory removal efficiency of TOC was achieved in spite of high salinity. • The initial pH plays the most significant role in the degradation of ML-GFW. The present study reports the use of the O₃/H₂O₂ process in the pretreatment of the mother liquor of gas field wastewater (ML-GFW), obtained from the multi-effect distillation treatment of the gas field wastewater. The range of optimal operation conditions was obtained by single-factor experiments. Response surface methodology (RSM) based on the central composite design (CCD) was used for the optimization procedure. A regression model with Total organic carbon (TOC) removal efficiency as the response value was established (R² = 0.9865). The three key factors were arranged according to their significance as: pH>H₂O₂ dosage>ozone flow rate. The model predicted that the best operation conditions could be obtained at a pH of 10.9, an ozone flow rate of 0.8 L/min, and H₂O₂ dosage of 6.2 mL. The dosing ratio of ozone was calculated to be 9.84 mg O₃/mg TOC. The maximum removal efficiency predicted was 75.9%, while the measured value was 72.3%. The relative deviation was found to be in an acceptable range. The ozone utilization and free radical quenching experiments showed that the addition of H₂O₂ promoted the decomposition of ozone to produce hydroxyl radicals (·OH). This also improved the ozone utilization efficiency. Gas chromatography-mass spectrometry (GC-MS) analysis showed that most of the organic matters in ML-GFW were degraded, while some residuals needed further treatment. This study provided the data and the necessary technical supports for further research on the treatment of ML-GFW.     

工程规模长填龄渗滤液膜生物-纳滤组合设施各单元污染物去除效能

填埋场渗滤液性质复杂,普遍采用生物处理与深度处理多单元串联工艺;但是,因缺乏对工程运行规模中各单元污染物处理贡献的评估数据,使优化单元组合方式缺少理论依据.因此,本文采用常规和荧光光谱指标结合的方法,对以采用"膜生物反应器（membrane biological reactor,MBR）+纳滤（nanofiltration,NF）"工艺、处理能力800 m³·d^-1的工程设施为对象,分析该组合工艺各单元对长填龄渗滤液处理贡献;同时,利用三维荧光-平行因子分析方法（excitation emission matrix fluorescence spectroscopy-parallel factor,EEM-PARAFAC）评估渗滤液中溶解性有机物（dissolved organic matters,DOM）性质的变化.结果表明,生物处理阶段对溶解性氮（dissolved nitrogen,DN）去除贡献率为74.7%,其中一级反硝化单元对DN去除贡献率为54.6%,外置式超滤单元对溶解性化学需氧量（dissolved chemical oxygen demand,sCOD）和溶解性碳（dissolved oganic carbon,DOC）降低贡献率分别为92.2%和93.3%,纳滤单元可有效去除重金属和盐分,但能力有限.通过追踪长填龄渗滤液DOM变化发现,一级反硝化单元可去除长填龄渗滤液中75.4%的类蛋白物质,超滤单元主要截留亲水性较高的DOM,而高芳香性的腐殖质主要通过纳滤截留,腐殖化程度越高截留效果越好.研究结果提示,处理长填龄渗滤液时,MBR工艺生物处理单元可适当简化,超滤单元则应预防堵塞.     

太湖不同生态型湖区悬浮颗粒磷空间分布和降解速率

对太湖不同生态型湖区水体悬浮颗粒物含量,有机磷组成及降解特征进行分析,研究了富营养化湖泊颗粒磷性质及其对水体磷循环的影响.太湖颗粒P平均占水体TP浓度的75.86％;不同生态类型湖区间颗粒物性质差异明显,河口区和湖心区的颗粒物含量高于藻型湖区和草型湖区,但颗粒物有机质比例分布却相反.利用³¹P液相核磁共振法（³¹P-NMR）发现太湖悬浮颗粒P的成分包括膦酸酯,正磷酸盐,磷酸单酯,磷酸二酯,焦磷酸盐和多聚磷酸盐6类,含量分别为1.06%,50.99%,33.02%,2.48%,10.68%和3.80%.不同生态型湖区之间颗粒P组成差异明显,河口区正磷酸盐含量最高,达到82.57%,藻型湖区和湖心区颗粒有机磷比例最高,分别达到达到 64.02%和63.95%;颗粒物焦磷酸盐和多聚磷酸盐可能以藻源性颗粒物来源为分别与Chla浓度呈显著相关（P<0.05; P<0.01）.颗粒态生物可利用性磷（PEHP）与正磷酸盐显著相关（P<0.05）,说明颗粒物正磷酸盐是颗粒物生物可利用性磷的重要来源.太湖PEHP降解速率平均为47.3min,PEHP占水体生物可利用磷（EHP）的65.16%,说明颗粒P是水体溶解性反应磷（SRP）补充的重要来源.     

Metal characterization of airborne particulate matters in a coastal region

The concentrations of suspended particulate matter in the air of the Orissa Sand Complex had an average value of 128 ± 10 µg m^?3 in residential areas and 170 ± 8 µg m^?3 in mining areas. PM₁₀ levels in residential areas were found to have an average of 35 ± 10 µg m^?3, in mining areas 45 ± 10 µg m^?3. The distribution of some elements is also discussed here. Inhalation doses were observed to be higher in summer than in winter and the rainy season. The highest dose rate was for the age group of 1 year, and health risks were found to be highest for the same. For adults, inhalation dose and health risk are 1.3 times higher in mining than in residential areas.     

DOC+CDPF对生物柴油燃烧颗粒排放特性的影响

以一台满足国五排放法规的车用柴油机为样机,研究加装氧化催化转化器DOC与催化型颗粒捕集器CDPF(DOC+CDPF后处理装置)前后,柴油机燃用B20燃料(燃料含20%体积掺混比的生物柴油)的颗粒排放特性.结果表明,在未加装该后处理装置时,该机排气颗粒数量浓度的粒径分布呈双峰形态,B20燃料的排气颗粒数量浓度的峰值粒径在10nm和50nm附近,纯柴油的排气颗粒数量浓度的峰值粒径在50nm和200nm附近.在颗粒粒径小于120nm的区域,该机燃用B20燃料的排气颗粒数量浓度大于纯柴油.加装该后处理装置后,该机排气颗粒数量浓度的粒径分布呈多峰形态,峰值粒径在10nm、20nm和60nm附近.加装DOC+CDPF后,不论是柴油还是B20燃料,与原机相比,柴油机排气颗粒总数量下降明显,其中60~200nm粒径范围的颗粒数量浓度降幅更为显著.在相同工况下,DOC+CDPF对柴油机燃用B20燃料的颗粒总数量净化效率高于纯柴油.     

黄河下游水体悬浮颗粒物中金属元素的地球化学行为

为调查黄河下游颗粒物的风化状况以及重金属变化规律及其污染程度,于2009年6~7月调水调沙期间(每日)及2010年4月至2011年11月(每月中旬)对垦利浮桥水体颗粒物进行采样调查.样品经消解后采用ICP-AES测定其中Al、Na、K、Ca、Fe、Mn、Cu、Zn、Cr、Ni、V的含量.采用化学风化指数(CIA)来衡量硅酸盐的化学风化程度,结果表明,黄河流域颗粒物化学风化程度为中等,近30年来颗粒物化学风化程度没有明显变化.黄河下游颗粒物中重金属(Cu、Zn、Cr、Ni、V)浓度呈现出冬季高夏季低的变化规律,调水调沙期间重金属浓度降低后期略有回升,这一变化规律主要是受泥沙的稀释及颗粒物粒径等因素影响.重金属富集因子(EF)的计算表明,黄河下游Zn具有中等程度的污染,其他元素无明显污染.提取3个因子对黄河下游颗粒物的化学组成因素进行分析,颗粒物主要受风化的影响,同时也受径流量以及人类活动的影响.     

太湖中颗粒有机碳对水体固有光学特性的影响

利用2011年5期太湖现场测量数据和室内分析数据,通过建立ρ(POC)(POC为颗粒有机碳)与a_p(λ)(颗粒物吸收系数)、b_bp(510)(总颗粒物的后向散射系数)的相关关系,评价了POC对水体固有光学特性的影响. 结果表明,太湖水体ρ(POC)时空变化显著,各期样品平均值在1 558.06~5 281.09 mg/m3之间变化. ρ(POC)与a_p(λ)具有较好的相关关系,特别是在浮游植物色素强烈吸收的波段(605~700 nm),各期数据的相关系数均在0.9以上;但ρ(POC)与b_bp(510)的相关性较差(R2=0.04, P=0.02). 进一步分析ρ(POC)对颗粒物的色素部分和非色素部分的影响发现,ρ(POC)与色素颗粒物吸收系数〔a_ph(665)〕的相关性很好(R2=0.82),而与非色素颗粒物吸收系数相关性较差. ρ(NPOC)(NPOC为非有机碳颗粒物)与b_bp(510)的相关性较好(R2>0.60),说明太湖水体POC对浮游植物色素的吸光特性有重要影响,而NPOC影响了水体的后向散射特性.      

Mass concentrations and temporal profiles of PM10, PM2.5 and PM1 near major urban roads in Beijing

Mass concentrations of PM₁₀, PM_2.5 and PM₁ were measured near major roads in Beijing during six periods: summer and winter of 2001, winter of 2007, and periods before, during and after the 2008 Beijing Olympic Games. Since the control efforts for motor vehicles helped offset the increase of emissions from the rapid growth of vehicles, the averaged PM_2.5 concentrations at roadsides during the sampling period between 2001 and 2008 fluctuated over a relatively small range. With the implementation of temporary traffic control measures during the Olympics, a clear “V” shaped curve showing the concentrations of particulate matter and other gaseous air pollutants at roadsides over time was identified. The average concentrations of PM₁₀, PM_2.5, CO and NO decreased by 31.2%, 46.3%, 32.3% and 35.4%, respectively, from June to August; this was followed by a rebound of all air pollutants in December 2008. Daily PM₁₀ concentrations near major roads exceeded the National Ambient Air Quality Standard (Grade II) for 61.2% of the days in the non-Olympic periods, while only for 12.5% during the Olympics. The mean ratio of PM_2.5/PM₁₀ near major roads remained relatively stable at 0.55 (±0.108) on non-Olympic days. The ratio decreased to 0.48 (±0.099) during the Olympics due to a greater decline in fine particles than in coarse-mode PM. The ratios PM₁/PM_2.5 fluctuated over a wide range and were statistically different from each other during the sampling periods. The average ratios of PM₁/PM_2.5 on non-Olympic days were 0.71.     

民用燃料燃烧排放PM2.5和PM10中碳组分排放因子对比

在实验室中模拟民用燃料在家庭炉灶中的燃烧,应用稀释通道系统采集颗粒物,获得玉米秸秆、薪柴、蜂窝煤和块煤四种常用民用燃料燃烧排放PM10,PM2.5及载带碳组分的排放因子.结果表明,民用燃料燃烧排放的颗粒物以细颗粒为主, PM2.5占PM10的70%~90%.颗粒物排放因子最大的为块煤,其PM2.5和PM10的排放因子分别为9.837和11.929g/kg,分别是蜂窝煤的12.6和13.7倍;玉米秸秆和薪柴PM2.5和PM10的排放因子稍低于块煤,为7.359~10.444g/kg.4种燃料燃烧OC排放因子块煤最高,其在PM2.5和PM10中分别为5.29和5.19g/kg.薪柴燃烧EC的排放因子最高,其在PM2.5和PM10 中的排放因子分别为1.065和1.126g/kg.块煤两种粒径上EC的排放因子略低于薪柴.蜂窝煤EC的排放因子最低,比薪柴低300倍左右,玉米秸秆EC的排放因子也要比薪柴低10倍左右.碳组分是块煤,秸秆,薪柴排放颗粒物的主要成分,其含量在40%~60%之间,该值比蜂窝煤高3倍.四种燃料对应的OC/EC比值差异很大,薪柴和块煤燃烧排放颗粒该值为3~6,秸秆和蜂窝煤燃烧排放颗粒其值高达30~50.     

2000~2011年深圳湾及邻近水域颗粒有机物的来源和时空分布

依据2000~2011年每月一次的调查资料,简要描述和讨论了深圳湾及邻近水域中颗粒有机物(POM)质量浓度的时空分布,并结合盐度和叶绿素a (Chl a)实测数据探讨POM的来源和滞留时间.结果表明深圳湾的POM质量浓度和陆源质量分数分别约为4.2mg/L,79%,而伶仃洋东部沿岸的分别约为1.9mg/L,42%.深圳湾和伶仃洋东部沿岸中现存浮游植物颗粒有机物(PPOM):Chl a比率分别约为92,54g/g,由此估算的PPOM质量浓度分别为0.8,0.2mg/L左右.依据浮游植物生产力和累计海源POM估算的POM滞留时间在深圳湾中为1~5d,而在伶仃洋东部沿岸中约为10d.研究期间伶仃洋东部沿岸POM质量浓度的年际变化略呈上升趋势,从1.7mg/L上升至2.0mg/L;深圳湾POM质量浓度在2000~2005年呈上升趋势,从3.0mg/L上升至5.5mg/L,在2006~2011年则呈下降趋势,从5.4mg/L下降至3.0mg/L.