Degradation of chlorinated phenols by nanoscale zero-valent iron

Chlorophenols (CPs), as important contaminants in groundwater, are toxic and difficult to biodegrade. Recently nanoscale zero-valent iron received a great deal of attention because of its excellent performance in treating recalcitrant compounds. In this study, nanoscale zero-valent iron particles were prepared using chemical reduction, and the reductive transformations of three kinds of chlorinated phenols (2-CP, 3-CP, and 4-CP) by nanoscale zero-valent iron under different conditions were investigated. The transformation process of the CPs was shown to be dechlorination first, then cleavage of the benzene ring. The removal efficiency of the CPs varied as follows: 2-CP > 3-CP > 4-CP. The reactivity of CPs was associated with their energy of lowest unoccupied molecular orbit (E _LUMO). With the increase in initial concentrations of CPs, removal efficiency decreased a little. But the quantities of CPs reduced increased evidently. Temperature had influence on not only the removal efficiency, but also the transformation pathway. At higher temperatures, dechlorination occurred prior to benzene ring cleavage. At lower temperatures, however, the oxidation product was formed more easily. __________ Translated from China Environmental Science, 2006, 26(6): 698–702 [译自: 中国环境科学]     

钢铁生产行业二英污染特征变化及其排放因子

对我国某省多家钢铁生产企业烧结工序和电炉工序排放烟气中二英（PCDD/Fs）污染水平、排放特征及其排放因子进行了初步研究.结果表明,烧结工序PCDD/Fs毒性当量浓度（以I-TEQ计,下同）为0.003~0.557 ng·m^-3,均值为0.165 ng·m^-3;电炉工序PCDD/Fs毒性当量浓度为0.006~0.057 ng·m^-3,均值为0.025 ng·m^-3.PCDD/Fs毒性当量浓度水平总体较低,较2005~2019年研究报道结果下降1~2个数量级.2005~2020年,钢铁生产行业排放PCDD/Fs毒性当量浓度水平先升高后降低,尤其是新的标准限值实施以及对烟尘等常规污染物进行超低排放控制后,呈现大幅下降.指纹谱图特征显示,所有烟气样品17种PCDD/Fs中最大浓度贡献单体为2,3,7,8-TCDF,与已有研究中以高氯代PCDFs和PCDDs为主不同,且低氯代PCDFs占比有所增加,表明PCDD/Fs生成主要来源有所变化.烧结工序和电炉工序PCDD/Fs同类物指纹分布特征相似,呈现典型的高温热过程特征,两个工序生产过程中PCDD/Fs的生成机制可能均为"从头合成".钢铁生产企业烧结工序PCDD/Fs废气排放因子（以I-TEQ计,下同）为0.003~0.5 μg·t^-1,排放因子平均值为（0.18±0.22）μg·t^-1;电炉工序PCDD/Fs废气排放因子为0.04~0.5 μg·t^-1,排放因子平均值为（0.27±0.23）μg·t^-1;低于UNEP于2013发布的"二英和呋喃排放识别和量化标准工具包"以及2004年我国二英排放清单中的排放因子,建议对我国钢铁生产行业PCDD/Fs排放状况开展调查,更新排放因子.     

硅肥等量施用对土壤镉生物有效性和水稻吸收镉的影响

为研究硅（Si）肥等量施用对水稻不同生育期吸收镉（Cd）和土壤Cd生物有效性的影响,采用5种不同种类的Si肥（SiO₂用量为225 kg ·hm^-2）开展田间小区试验.结果表明,随着水稻生育期的延长,水稻根系和茎叶的Cd含量增加;施用Si肥,不同生育期水稻根系、茎叶和籽粒Cd含量平均分别降低14.9%、28.2%和12.2%;硅钙镁铁肥（SiCaMgFe）和水溶Si肥（SiW）处理,籽粒Cd含量分别比对照处理降低21.1%（P<0.05）和21.2%（P<0.05）;水稻根表铁膜中Cd含量（DCB-Cd）随着水稻生育期延长而增加,施用Si肥,水稻不同生育期DCB-Cd含量有高有低,DCB-Cd是根系Cd含量的15.8%~42.8%;与对照相比,施用Si肥水稻成熟期土壤可交换态Cd （Exc-Cd）含量平均降低36.4%,其它形态的含量平均增加12.5%~48.2%.水稻全生育期根系Cd与Si呈极显著负相关,与DCB-Cd呈极显著正相关,DCB-Cd与土壤有效态Cd和有效态Si呈极显著负相关,土壤Exc-Cd与Carb-Cd呈极显著负相关,土壤有效态Cd与pH值呈显著负相关.施用相同Si肥用量,SiCaMgFe和SiW处理降低水稻Cd含量的效果好;施用Si肥通过提高土壤pH值和土壤有效Si含量、降低土壤有效态Cd和Exc-Cd含量,促进Exc-Cd向Carb-Cd转移,减少根表铁膜对Cd的吸附,从而减少水稻对土壤Cd的吸收.     

Ligand-assisted degradation of carbon tetrachloride by microscale zero-valent iron

Degradation of carbon tetrachloride (CT) by microscale zero-valent iron (ZVI) was investigated in batch systems with or without organic ligands (ethylenediaminetetraacetic acid (EDTA), citric acid, tartaric acid, malic acid and oxalic acid) at pHs from 3.5 to 7.5. The results demonstrated that at 25°C, the dechlorination of CT by microscale ZVI is slow in the absence of organic ligands, with a pseudo-first-order rate constant of 0.0217 h(-1) at pH 3.5 and being further dropped to 0.0052 h(-1) at pH 7.5. However, addition of organic ligands significantly enhanced the rates and the extents of CT removal, as indicated by the rate constant increases of 39, 31, 32, 28 and 18 times in the presence of EDTA, citric acid, tartaric acid, malic acid and oxalic acid, respectively, at pH 3.5 and 25°C. The effect of EDTA was most significant; the dechlorination of CT at an initial concentration of 20 mg l(-1) increased from 16.3% (no ligands) to 89.1% (with EDTA) at the end of 8h reaction. The enhanced CT degradation in the presence of organic ligands was primarily attributed to the elimination of a surface passivation layer of Fe(III) (hydr)oxides on the microscale ZVI through chelating of organic ligands with Fe(III), which maintained the exposure of active sites on ZVI surface to CT.     

腐殖酸与钙离子共存下ZVI界面沉积过程

为精准分析环境介质在零价铁（ZVI）界面沉积过程和沉积层特性,采用喷涂方法制备ZVI负载芯片,应用耗散式石英晶体微天平（QCMD）研究了腐殖酸（HA）与钙离子（Ca（Ⅱ））在ZVI界面沉积吸附过程的差异,并探讨了Ca（Ⅱ）浓度与HA/Ca（Ⅱ）投加顺序对沉积过程的影响机理.结果表明,在反应体系中先通入HA相较先通入Ca（Ⅱ）,ZVI表面形成的沉积层质量更高、沉积层结构更稳定;HA沉积后可促进Ca（Ⅱ）沉积,然而Ca（Ⅱ）先沉积后HA沉积量较少,很大程度上与吸附层外层结构组成差异相关.此外,发现随着Ca（Ⅱ）浓度从10mg/L升高至200mg/L,Ca（Ⅱ）沉积速率加快,界面沉积量增多.QCMD耗散变化研究发现,当Ca（Ⅱ）浓度从10mg/L提高至100mg/L,沉积层耗散变化值（ΔD）逐渐下降,沉积层转变为刚性结构;Ca（Ⅱ）浓度继续加大到200mg/L,ΔD升高趋势,沉积层构象呈现疏松态.应用QCMD可实时监测ZVI钝化层形成的动态变化过程,提供了ZVI界面吸附层变化特征等关键信息.     

新冠期间河北省典型钢铁企业大气污染影响

基于国家气象局气象预报数据,建立了基于AERMOD的钢铁企业污染预报模型,模拟了新冠疫情管控期（2020年2~3月）及解封后期（2020年4~10月）河北省某钢铁企业对大气污染的影响,并结合空气质量实测数据进行模型验证.结果显示,不利风向条件下,该钢铁厂大气污染物排放对当地3个国控站点SO₂、NO_x和PM₁₀的平均浓度贡献占比,在疫情管控期分别为20.19%~33.81%,17.49%~23.46%和2.02%~2.69%,在解封后期分别为13.43%~21.01%,11.09%~20.92%和1.20%~2.22%.由于疫情管控期受其他人为源干扰较少,该钢铁厂SO₂、NO_x和PM₁₀的预报值和三个国控站点实际监测值的相关系数,在新冠疫情管控期（在单个站点中,最高分别为0.43、0.48和0.29）高于解封后期（最高分别为0.42、0.39和0.07）.     

零价铁修复1,3-二氯苯污染底泥

通过序批试验研究了零价铁修复对底泥中1,3-二氯苯的去除效果,分析了零价铁修复过程中pH和铁离子质量浓度以及修复后底泥土壤酶的恢复情况. 结果表明:添加占底泥干质量2%的还原铁粉,1,3-二氯苯的去除率可达72.3%〔初始w(1,3-二氯苯)为500 　mg/kg,培养时间为20 d〕,较未添加零价铁修复处理高52.0%. 零价铁有效地促进了底泥中1,3-二氯苯的去除,土著微生物在自然恢复中起一定的作用. 在修复过程中零价铁并未使底泥pH发生明显变化,底泥水体中的总铁质量浓度(低于0.3 mg/L)始终符合地表水环境质量标准(GB3838—2002). 1,3-二氯苯污染使底泥过氧化氢酶、转化酶和蛋白酶的酶活性显著降低,使脲酶的酶活性显著升高. 零价铁修复使1,3-二氯苯抑制的底泥过氧化氢酶的酶活性恢复到未污染对照水平.      

酸浸粉煤灰混凝法处理制革废水的研究

笔者研究了在热电厂粉煤灰中加入少量的鼓风炉铁泥和适量的助溶剂HS,在加热条件下用稀硫酸搅拌浸取2h后,制得集物理吸附和化学混凝为一体的混凝剂。这种混凝剂与聚硅酸铝铁(PSAF)絮凝剂配合处理COD为1500～2000mg/L制革废水,SS,COD,硫化物和铬的去除率分别为95%,93%,92%和88%。该法的显著特点是混凝沉降速度快,污泥体积小,处理废水费用低,此外还探讨了酸浸粉煤灰混凝剂对制革废水的混凝沉降机理。      

利用废铁屑处理含铬废水试验研究

通过研究在酸性条件下利用废铁屑处理剧毒的六价铬电镀废水的工艺条件 ,在最佳条件下废水中六价铬去除率达99 %以上 ,出水总铬含量为0.040mg/l,六价铬含量为0.002mg/l,大大低于国家排放标准0.500mg/l。     

In situ sequential treatment of a mixed contaminant plume

Groundwater plumes often contain a mixture of contaminants that cannot easily be remediated in situ using a single technology. The purpose of this research was to evaluate an in situ treatment sequence for the control of a mixed organic plume (chlorinated ethenes and petroleum hydrocarbons) within a Funnel-and-Gate. A shallow plume located in the unconfined aquifer at Alameda Point, CA, was found to contain up to 218,000 μg/l of cis-1,2 dichloroethene (cDCE), 16,000 μg/l of vinyl chloride (VC) and <1000 μg/l of 1,1 dichloroethene (1,1 DCE), trans-1,2 dichloroethene (trans-1,2 DCE) and trichloroethene (TCE). Total benzene, toluene, ethylbenzene and xylenes (BTEX) concentrations were <10,000 μg/l. Contaminated groundwater was funneled into a gate, 3.0 m wide, 4.5 m long and 6.0 m deep (keyed into the underlying aquitard) where treatment occurred. The initial gate segment consisted of granular iron, for the reductive dechlorination of the higher chlorinated ethenes. The second segment, the biosparge zone, promoted aerobic biodegradation of petroleum hydrocarbons and any remaining lesser-chlorinated compounds, stimulated by dissolved oxygen (DO) and carbon dioxide (CO₂) additions via an in situ sparge system (CO₂ was used to neutralize the high pH produced from reactions in the iron wall). Groundwater was drawn through the gate by pumping two wells located at the sealed, downgradient, end. Over a 4-month period an estimated 1350 g of cDCE flowed into the treatment gate and the iron wall removed 1230 g, or 91% of the mass. The influent mass of VC was 572 g and the iron wall removed 535 g, corresponding to 94% mass removal. The other chlorinated ethenes had significantly lower influent masses (3 to 108 g) and the iron wall removed the majority of the mass resulting in >96% mass removal for any of the compounds. In spite of these high removal percentages, laboratory column tests indicated that at these levels of chlorinated contaminants, surface saturation of the iron grains likely contributed to lower than expected reaction rates. In the biosparge zone, mass removal of cDCE appeared to occur predominantly by biodegradation (65%) with volatilization (35%) being an important secondary process. The dominant removal process for VC was volatilization (70%) although significant biodegradation was also indicated (30%). Laboratory microcosm results confirmed the potential for aerobic biodegradation of cDCE and VC. When average influent field concentrations for cDCE and VC were 220,000 and 46,000 μg/l, respectively, the sequential treatment unit removed 99.6% of the total mass and when the influent concentrations decreased to 26,000 and 19,000 μg/l for cDCE and VC, respectively, >99.9% removal within the treatment gate was attained. BTEX compounds were found to be significantly retarded in the iron treatment zone. Although they did eventually break through the granular iron, and into the gravel transition zone, none of these compounds was detected in the biosparge zone. No noticeable interferences between the anaerobic (reductive) and aerobic parts of the system occurred during testing. The results of this experiment show that in situ treatment sequences are viable, although further work is needed to optimize performance.