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.     

阳澄湖水源中典型嗅味物质测定与来源分析

以阳澄湖水源为研究对象,采用固相微萃取-气质联用法测定水中2-甲基异莰醇(2-MIB)、土臭素(GSM)、2,4,6-三氯苯甲醚(2,4,6-TAC)、2,3,4-三氯苯甲醚(2,3,4-TAC)、2,3,6-三氯苯甲醚(2,3,6-TAC)、2-异丙基-3甲氧基吡嗪(IPMP)、2-异丁基-3甲氧基吡嗪(IBMP)、β-环柠檬醛、β-紫罗兰酮、异氟尔酮等10种典型嗅味物质,并分析可能的来源藻类.以2018年1月-12月阳澄湖水源中优势藻种为基础,建立以上述嗅味物质为变量的多元线性回归模型.结果表明,水源中2-MIB、GSM、β-环柠檬醛、β-紫罗兰酮、异氟尔酮5种嗅味物质与直链藻、针杆藻、鱼腥藻、色球藻、颤藻、微囊藻、束丝藻7种藻类有较强的相关性.     

The performance of nitrate-reducing Fe(II) oxidation processes under variable initial Fe/N ratios: The fate of nitrogen and iron species

•Bacterially-mediated coupled N and Fe processes examined in incubation experiments. •NO₃⁻ reduction was considerably inhibited as initial Fe/N ratio increased. •The maximum production of N₂ occurred at an initial Fe/N molar ratio of 6. •Fe minerals produced at Fe/N ratios of 1–2 were mainly easily reducible oxides. The Fe/N ratio is an important control on nitrate-reducing Fe(II) oxidation processes that occur both in the aquatic environment and in wastewater treatment systems. The response of nitrate reduction, Fe oxidation, and mineral production to different initial Fe/N molar ratios in the presence of Paracoccus denitrificans was investigated in 132 h incubation experiments. A decrease in the nitrate reduction rate at 12 h occurred as the Fe/N ratio increased. Accumulated nitrite concentration at Fe/N ratios of 2–10 peaked at 12–84 h, and then decreased continuously to less than 0.1 mmol/L at the end of incubation. N₂O emission was promoted by high Fe/N ratios. Maximum production of N₂ occurred at a Fe/N ratio of 6, in parallel with the highest mole proportion of N₂ resulting from the reduction of nitrate (81.2%). XRD analysis and sequential extraction demonstrated that the main Fe minerals obtained from Fe(II) oxidation were easily reducible oxides such as ferrihydrite (at Fe/N ratios of 1–2), and easily reducible oxides and reducible oxides (at Fe/N ratios of 3–10). The results suggest that Fe/N ratio potentially plays a critical role in regulating N₂, N₂O emissions and Fe mineral formation in nitrate-reducing Fe(II) oxidation processes.     

Sewage sludge ditch for recovering heavy metals can improve crop yield and soil environmental quality

• Indirect use of sludge in ditches alongside plants was tested in field experiments. • The dried and stabilized sludge in ditches was recovered with heavy metals. • Cd, Pb, Cu and Zn in the planted soil were all in a safe range. • The indirect use of sludge increased plant yield, soil N content and C storage. The treatment and disposal of municipal sewage sludge (MSS) is an urgent problem to be resolved in many countries. Safely using the nutrients within MSS to increase crop yield and enhance the fertility of poor soil could contribute to achieving sustainable development. An indirect use of MSS in ditches alongside Pennisetum hybridum plants was studied in field plots for 30 months and the contents of heavy metals and macronutrients were monitored in soil, sludge and plant samples. We found that the yield of P. hybridum was significantly increased by 2.39 to 2.80 times and the treated plants had higher N content compared with no sludge. In addition, the organic matter (OM) and N contents in the planted soil increased significantly compared with the initial soil. The OM content in the planted soil of the MSS treatment was 2.9 to 5.2 times higher than that with no sludge, and N increased by 2.0 to 3.8 times. However, MSS had no significant effect on the N, P and K contents in the soil at the bottom of the MSS ditch, and the content of heavy metals (Cd, Pb, Cu and Zn) were also within the safe range. Moreover, the moisture content and phytotoxicity of MSS after this indirect use were reduced and the heavy metal contents changed little, which is favorable to the further disposal of recovered MSS. Therefore, this indirect use of MSS is beneficial to agricultural production, soil quality and environmental sustainability.     

液液萃取-气相色谱/串联质谱法测定水中五氯酚及其钠盐

采用液液萃取处理水样,用气相色谱-串联质谱法测定样品中五氯酚及其钠盐,通过优化测定条件,使方法在1.00μg/L~500μg/L范围内线性良好。检出限和定量限分别为1.00μg/L和5.00μg/L,空白水样五氯酚钠3个质量浓度水平的加标回收率为89.8%~98.4%,5次平行试验测定结果的RSD为5.5%~10.7%。     

A/O-电催化氧化法处理中转站垃圾渗滤液

采用A/O-电催化氧化法处理村镇垃圾中转站渗滤液，并针对工艺核心电催化氧化单元的相关运行参数进行探究。结果表明：使用椰壳活性炭作为粒子电极基体材料，以Sn-Sb作为活性催化剂，在初始pH值＜7、外加电压15 V条件下，电解中转站垃圾渗滤液效果较好；联合工艺连续运行阶段，当水力停留时间达到11 d时，原水COD从（31 098±1 270）mg/L下降到（391±44）mg/L，渗滤液可生化性（B/C）从0.336±0.020提升到0.719±0.024，可生化性显著增强。     

Temporal trends in agricultural water use and the relationships to hydroclimatic factors in the High Plains aquifer region

The High Plains aquifer (HPA) is the primary water source for agricultural irrigation in the US Great Plains. The water levels in many locations of the aquifer have declined steadily over the past several decades because the rate of water withdrawals exceeds recharge, which has been a serious concern to the water resources management in the region. We evaluated temporal trends and variations in agricultural water use and hydroclimatic variables including precipitation, air temperature, reference evapotranspiration, runoff, groundwater level, and terrestrial water storage across the HPA region for different periods from 1985 to 2020 at the grid, county, or region scale. The results showed that water withdrawals decreased from 21.3 km³/year in 1985 to 18.2 km³/year in 2015, while irrigated croplands increased from 71,928 km² in 1985 to 78,464 km² in 2015 in the entire HPA. The hydroclimatic time-series showed wetting trends in most of the northern HPA, but drying and warming trends in the southern region from 1985 to 2020. The groundwater level time-series indicated flat trends in the north, but significant declining in the central and southern HPA. Trends in irrigation water withdrawals and irrigation area across the HPA were controlled by the advancement of irrigation systems and technologies and the management of sustainable water use, but also were affected by dynamical changes in the hydroclimatic conditions.     

典型地区农用地污染调查及风险管控标准探讨

针对《土壤污染风险管控标准——农用地土壤污染风险管控标准》(GB 15618—2018),提出以土壤中全量浓度筛选值和管控值作为衡量农用地土壤污染风险管控的标准,对湖南省部分稻田农用地土壤及点对点稻米样品中镉、铅、砷、汞的总量和有效态浓度及稻米中含量进行监测,根据重金属总量浓度分为低风险、中风险、高风险3组。结果显示:(1)土壤及稻米中镉含量基本为随着风险级别的升高而增加,铅、砷在土壤和稻米中含量无规律性结果,汞监测结果均为未检出。(2)低风险组稻米镉超标率为12. 0%,高风险组稻米镉达标率为33. 3%,表明利用总量浓度对农用地土壤潜在风险进行分组存在一定的局限性。(3)依据4种重金属在土壤中总量及稻米(早稻)中含量情况,对风险级别进行调整并综合判断:有58个样品为低风险组,占样品总数的68. 2%,超标率为零;有15个样品为中风险组,占样品总数的17. 7%,超标率为80. 0%;有12个样品为高风险组,占样品总数的14. 1%,超标率为100. 0%。调整后评价结果与上述标准的划分目标更接近,能够提高上述标准的准确性和实用性。     

三峡库区笋溪河流域面源污染及其与土壤可蚀性k值的关系

研究三峡库区面源污染特征及其与水土流失的关系,可为库区氮磷污染和土壤侵蚀控制提供依据.选择三峡库区库尾笋溪河流域,在流域内分园地、林地和耕地3种土地利用类型共采集126个土壤样品,并在主干和支流采集52个水质样品.根据EPIC模型计算土壤可蚀性k值,分析流域内土壤可蚀性k值对面源污染的影响.结果表明,笋溪河流域面源污染主要是氮污染,总氮均值达1.37 mg/L,氮素的主要形态为硝态氮,占总氮的71.2%;总磷浓度为0.1 mg/L.流域内土壤可蚀性k值均值为0.040,随着土层加深土壤可蚀性k值呈上升趋势;林地土壤可蚀性k值显著低于园地和耕地.笋溪河流域总氮浓度与园地和耕地0-20 cm土壤可蚀性k值有关,硝态氮浓度与耕地0-40 cm土壤可蚀性k值有关.因此,笋溪河流域面源污染严重,主要来源是耕地和园地,应实行免耕、植物篱等措施,同时减少化肥施用,增加有机肥比例,以增加土壤抗侵蚀能力,进而控制流域水土流失和面源污染.(图6参37)     

Ozone facilitated degradation of caffeine using Ce-TiO2 catalyst

The ozone initiated oxidation of 1,3,7-trimethylxanthine (caffeine), commonly found in wastewaters as model compound is reported using cerium (Ce)/titanium dioxide (TiO₂) as catalyst. The effect of pH and loading of ceria on titania were investigated. Effect of reaction conditions on degradation of caffeine based on their pseudo first-order rate constants were compared. The combination of catalyst Ce-TiO₂ and ozone aeration significantly enhanced the degradation of caffeine compared to uncatalysed ozonation. The oxidation of caffeine ensued via the free radical mechanism, through enhanced ozone decomposition into OH radicals. Ce/TiO₂(0.5?wt%) showed good activity in degradation of caffeine at pH 6, in both natural stream and river water samples showing about 60% total organic carbon removal in 2?h ozonation period. Using liquid chromatography-mass spectroscopy, degradation products were analysed. A reaction intermediate and one final product were positively identified. Nano-catalysts with different loadings of Ce on TiO₂ synthesized by sol-gel route were characterized by scanning electron microscope, transmission electron microscopy, BET and powder X-ray diffraction spectrum techniques. The results showed that the material retained a highly ordered mesoporous structure and possessed large surface area.