Enhanced carbon tetrachloride degradation by hydroxylamine in ferrous ion activated calcium peroxide in the presence of formic acid

• Complete CT degradation was achieved by employing HA to CP/Fe(II)/FA process. • Quantitative detection of Fe(II) regeneration and HO• production was investigated. • Benzoic acid outcompeted FA for the reaction with HO•. • CO₂•⁻ was the dominant reductive radical for CT removal. • Effects of solution matrix on CT removal were conducted. Hydroxyl radicals (HO•) show low reactivity with perchlorinated hydrocarbons, such as carbon tetrachloride (CT), in conventional Fenton reactions, therefore, the generation of reductive radicals has attracted increasing attention. This study investigated the enhancement of CT degradation by the synergistic effects of hydroxylamine (HA) and formic acid (FA) (initial [CT] = 0.13 mmol/L) in a Fe(II) activated calcium peroxide (CP) Fenton process. CT degradation increased from 56.6% to 99.9% with the addition of 0.78 mmol/L HA to the CP/Fe(II)/FA/CT process in a molar ratio of 12/6/12/1. The results also showed that the presence of HA enhanced the regeneration of Fe(II) from Fe(III), and the production of HO• increased one-fold when employing benzoic acid as the HO• probe. Additionally, FA slightly improves the production of HO•. A study of the mechanism confirmed that the carbon dioxide radical (CO₂•⁻), a strong reductant generated by the reaction between FA and HO•, was the dominant radical responsible for CT degradation. Almost complete CT dechlorination was achieved in the process. The presence of humic acid and chloride ion slightly decreased CT removal, while high doses of bicarbonate and high pH inhibited CT degradation. This study helps us to better understand the synergistic roles of FA and HA for HO• and CO₂•⁻ generation and the removal of perchlorinated hydrocarbons in modified Fenton systems.     

Degradation rates of aged petroleum hydrocarbons are likely to be mass transfer dependent in the field

Evidence for on site biodegradation may be difficult to provide at heterogeneous sites without additional experiments in controlled laboratory conditions. In this study, microbial activities measured as CO₂ and CH₄ production were compared in situ, in intact soil cores and in bottle microcosms containing sieved soils. In addition, biodegradation rates were determined by measuring the decrease in petroleum hydrocarbon concentrations at 7°C in aerobic and anaerobic conditions. Elevated concentrations of CO₂ and CH₄ in the soil gas phase indicated that both the aerobic and anaerobic microbial activity potentials were high at the contaminated site. Aerobic and anaerobic microbial degradation rates in laboratory experiments of petroleum hydrocarbons were highest in soils from the most contaminated point and degradation in the aerobic and anaerobic microcosms was linear throughout the incubation, indicating mass-transfer-dependent degradation. Different results for microbial activity measurements were obtained in laboratory studies depending on pretreatment and size of the sample, even when the environmental conditions were mimicked. These differences may be related to differences in the gas exchange rates as well as in changes in the bioavailability of the contaminant in different analyses. When predicting by modeling the behavior of an aged contaminant it is relevant to adapt the models in use to correspond to conditions relevant at the contaminated sites. The variables used in the models should be based on data from the site and on experiments performed using the original aged contaminant without any additions.     

小尺度水平上植被格局对城市绿地土壤污染物累积的影响

小尺度水平上土壤污染物累积特征不仅与人们的生活直接相关,与社区环境管理和园林规划也有密切联系。选择北京市五环内具有不同植被格局(围绕式、行列式、混合式和群点式)的典型居民区为研究对象,通过小区内绿地的多点布点,调查分析表层土壤中的7种重金属元素(Cr、Ni、Cu、Zn、Cd、Pb、Mn)和16种优先控制多环芳烃(PAHs)的浓度;探究小尺度水平上,植被格局对绿地土壤重金属及多环芳烃累积的影响。结果表明：Cu、Zn、Cd和Pb为主要的重金属污染物;居民区土壤中,16种多环芳烃总量(Σ₁₆PAHs)的浓度为88.1~2 844 μg·kg⁻¹,其主要来源于煤炭燃烧而非石油及其产物燃烧;行列式植被格局的绿地土壤中,主要重金属和PAHs污染物的浓度分布较为分散,高浓度污染物也往往出现在该类植被格局的土壤中;而群点式植被格局土壤中,主要重金属污染物以及本地指示性多环芳烃Ant、BaA和BaP的浓度中位值都较其他3种植被格局低。对行列式植被格局的小区进行土壤质量调查时,需要采集较多的样品数量才能获得代表性污染物浓度;同时,行列式植被格局有利于对污染物的截获,使绿地土壤起到吸纳污染物的作用,而群点式植被格局的绿地土壤环境质量较好,但是不利于发挥吸纳污染物的生态功能。     

Application of semipermeable membrane device for assessing toxicity in drinking water

Semipermeable membrane devices (SPMDs) mimic passive diffusive transport of bioavailable hydrophobic organic compounds through biological membranes and their partitioning between lipids and environmental levels. Our study was developed on a surface water treatment plant based in Turin, Northern Italy. The investigated plant treats Po River surface water and it supplies about 20% of the drinking water required by Turin city (about one million inhabitants). Surface water (input) and drinking water (output) were monitored with SPMDs from October 2001 to January 2004, over a period of 30 days. The contaminant residues, monthly extracted from SPMDs by dialysis in organic solvent, were tested with the Microtox^TM acute toxic test and with the Ames mutagenicity test. Same extracts were also analyzed with gaschromatography—mass spectrometry technique in order to characterise the organic pollutants sampled, especially Polycyclic Aromatic Hydrocarbons (PAHs).

Although the PAHs mean concentration is about one hundred times lower in the output samples, the mean toxic units are similar in drinking and surface water.

Our data indicate that the SPMD is a suitable tool to assess the possible toxicity in drinking water.     

多环芳烃污染土壤的微生物修复技术

对生物修复技术中的微生物进行了分类,并阐述了微生物生物降解土壤中多环芳烃（PAHs）的基本原理。在此基础上,分析了国内外微生物生物修复技术的发展概况,采用图示法重点综述了原位处理技术和非原位处理技术的工艺流程,并列举了相应的工程应用实例。     

燕山石化地区NMHC的特征研究

本文采用气相色谱－质谱联用方法，对燕山石化地区不同生产区域的大气样品，定量地进行非甲烷碳氢化合物（ＮＭＨＣ）的分类测定。本方法可以鉴定Ｃ２－Ｃ１１共六十多个色谱峰。实验表明，燕山石化地区烷烃、烯烃和芳香烃等各类碳氢化合物均具有较高浓度，是对ＮＭＨＣ有重要贡献的一个工业源。本文还参照各大气样品的不同来源，分析了ＮＭＨＣ的排放特征，从而确定了燕山石化区ＮＭＨＣ排放的典型物种。     

3种石油烃降解菌对石油烃的降解效果及其细胞表面疏水性

选取3种石油烃降解菌:假单胞菌(Pseudomonas sp.,DS-1)、铜绿色假单胞菌(Pseudomonas aeruginosa,DS-2)和无色杆菌(Achromobacter sp.,DS-3),研究其对石油烃的降解效果及其细胞表面疏水性。结果表明,经过6d的降解,3种石油烃降解菌对石油烃的降解率分别为99.08%、79.75%、84.34%。石油烃的黏附性测试和盐析聚集测试结果表明,3种石油烃降解菌均表现出较高的细胞表面疏水性,其规律为DS-1DS-3DS-2。其中DS-1的细胞表面疏水性最高,达65.90%。DS-1、DS-2和DS-3菌株发生盐析聚集所需最小(NH4)2SO4摩尔浓度分别为2.0、2.8、2.4 mol/L。菌株的细胞表面疏水性和降解有机物的能力有着较高的相关性。     

高压液相色谱(HPLC)测定油气田污染源中的多环芳烃

给出了高压液相色谱测定油气田污染源中多环芳烃方法的线性范围、检测下限、精密度、准确度、定性分析方法及实际样品的测定结果。     

北京地区表层土中饱和烃组成特征及成因分析

根据北京地区不同环境功能区62个样品检测结果,分析了研究区表层土壤中饱和烃类化合物的化学组成及其分布特征,并对其来源进行了讨论。结果表明：（1）北京地区表层土壤中分布有多种类型的烃类污染物,已检测到的饱和烃化合物主要包括正构烷烃、无环类异戊间二烯烷烃、单甲基取代支链烷烃（异构与反异构烷烃）、烷基环己烷和甾、萜烷类等系列化合物中的数百种单体化合物;（2）不同环境功能区,同一地区土地使用情况不同或周围环境不同的土壤样品中饱和烃的质量分数和组成特征均存在较大的差别,其中正构烷烃的质量分数为0.25~4.72μg.g-1;（3）随着距离城中心的距离减小,表土中饱和烃质量分数增高,南部地区饱和烃的质量分数高于北部地区;（4）表层土壤中饱和烃的来源比较复杂,主要来自于化石燃料及木材的不完全燃烧产物,部分地区有少量矿物油及其衍生物的输入。     

Catalytic fast pyrolysis of Kraft lignin with HZSM-5 zeolite for producing aromatic hydrocarbons

Catalytic fast pyrolysis (CFP) of Kraft lignins with HZSM-5 zeolite for producing aromatics was investigated using analytical pyrolysis methods. Two Kraft lignins were fast pyrolyzed in the absence and presence of HZSM-5 in a Curie-point pyrolyzer. Without the catalyst, fast pyrolysis of lignin predominantly produced phenols and guaiacols that were derived from the subunits of lignin. However, the presence of HZSM-5 changed the product distribution dramatically. As the SiO₂/Al₂O₃ ratio of HZSM-5 decreased from 200 to 25 and the catalyst-to-lignin ratio increased from 1 to 20, the lignin-derived oxygenates progressively decreased to trace and the aromatics increased substantially. The aromatic yield increased considerably as the pyrolysis temperature increased from 500°C to 650°C, but then decreased with yet further increase of pyrolysis temperature. Under optimal reaction conditions, the aromatic yields were 2.0 wt.% and 5.2 wt.% for the two lignins that had effective hydrogen indexes of 0.08 and 0.35.