Stable isotope fractionation analysis as a tool to monitor biodegradation in contaminated acquifers

The assessment of biodegradation in contaminated aquifers has become an issue of increasing importance in the recent years. To some extent, this can be related to the acceptance of intrinsic bioremediation or monitored natural attenuation as a means to manage contaminated sites. Among the few existing methods to detect biodegradation in the subsurface, stable isotope fractionation analysis (SIFA) is one of the most promising approaches which is pronounced by the drastically increasing number of applications. This review covers the recent laboratory and field studies assessing biodegradation of contaminants via stable isotope analysis. Stable isotope enrichment factors have been found that vary from no fractionation for dioxygenase reactions converting aromatic hydrocarbons over moderate fractionation by monooxygenase reactions (epsilon=-3 per thousand) and some anaerobic studies on microbial degradation of aromatic hydrocarbons (epsilon=-1.7 per thousand) to larger fractionations by anaerobic dehalogenation reactions of chlorinated solvents (epsilon=between -5 per thousand and -30 per thousand). The different isotope enrichment factors can be related to the respective biochemical reactions. Based on that knowledge, we discuss under what circumstances SIFA can be used for a qualitative or even a quantitative assessment of biodegradation in the environment. In a steadily increasing number of cases, it was possible to explain biodegradation processes in the field based on isotope enrichment factors obtained from laboratory experiments with pure cultures and measured isotope values from the field. The review will focus on the aerobic and anaerobic degradation of aromatic hydrocarbons and chlorinated solvents as the major contaminants of groundwater. Advances in the instrumental development for stable isotope analysis are only mentioned if it is important for the understanding of the application.     

Linear free energy relationships for dechlorination of aromatic chlorides by Pd/Fe

Reductive dechlorination rate constants for five chlorobenzenes in the presence of Pd/Fe as catalyst were determined experimentally. Linear free energy relationships (LFER) for the dechlorination rate constants of five chlorobenzenes and three chlorophenols were developed by partial least squares (PLS) regression based on quantum chemical parameters computed by PM3 Hamiltonian. The optimal LFER model obtained is

logk=−1.63+1.46×10⁻³ΔH_f−7.69×10⁻¹E_LUMO

where k stands for the dechlorination rate constants, ΔH_f is the standard heat of formation, and E_LUMO is the energy of the lowest unoccupied molecular orbital. The Q²_cum value of the model is 0.879, indicating good robustness and predictive power of the model.     

Formation of organic chloride in the treatment of textile dyeing sludge by Fenton system

In the oxidation treatment of textile dyeing sludge, the quantitative and transformation laws of organic chlorine are not clear enough. Thus, this study mainly evaluated the treatment of textile dyeing sludge by Fenton and Fenton-like system from the aspects of the influence of Cl⁻, the removal of polycyclic aromatic hydrocarbons (PAHs) and organic carbon, and the removal and formation mechanism of organic chlorine. The results showed that the organic halogen in sludge was mainly hydrophobic organic chlorine, and the content of adsorbable organic chlorine (AOCl) was 0.30 mg/g (dry sludge). In the Fenton system with pH=3, 500 mg/L Cl⁻, 30 mmol/L Fe²⁺ and 30 mmol/L H₂O₂, the removal of phenanthrene was promoted by chlorine radicals (•Cl), and the AOCl in sludge solid phase increased to 0.55 mg/g (dry sludge) at 30 min. According to spectral analysis, it was found that •Cl could chlorinate aromatic and aliphatic compounds (excluding PAHs) in solid phase at the same time, and eventually led to the accumulation of aromatic chlorides in solid phase. Strengthening the oxidation ability of Fenton system increased the formation of organic chlorines in liquid and solid phases. In weak acidity, the oxidation and desorption of superoxide anion promoted the removal and migration of PAHs and organic carbon in solid phase, and reduced the formation of total organic chlorine. The Fenton-like system dominated by non-hydroxyl radical could realize the mineralization of PAHs, organic carbon and organic chlorines instead of migration. This paper builds a basis for the selection of sludge conditioning methods.     

用二氧化氯降解废水中的苯胺类化合物（1）COD去除规律的研究

用二氧化氯氧化降解８种苯胺类化合物，测定了ＣＯＤ去除率与时间及ＣＯＤ去除率与ＣｌＯ２用量之间的关系；结果表明最终的ＣＯＤ去除率多数都在７０％以上，羟基类苯胺化合物可达９０％以上．反应符合ｌｎＣＯＤ＝Ｋ１ＷＣｌＯ２＋Ａ１及ｌｎＣＯＤｔ＝Ｋ２ｔ＋Ａ关系式．ＣＯＤ去除率还与ｐＨ值的大小有一定的相关性．     

Physicochemical and toxicological characteristics of nanoparticles in aerosols in southern Thailand during recent haze episodes in lower southeast Asia

Transboundary haze from biomass burning is one of the most important air pollutions in Southeast Asia. The most recent serious haze episode occurred in 2015. Southern Thailand was affected by the haze during September to October when the particulate matter concentration hit a record high. We investigated physical and chemical characteristics of aerosols, including concentration and aerosol size distribution down to sub-micron sizes during haze episodes in 2013 and 2015 and, for reference, an insignificant haze period in 2017. The highest total suspended particulates and PM₁₀ levels in Hat Yai city were 340.1 and 322.5 µg/m³. The mass fractions were nanoparticles (< 100 nm) 3.1%-14.8% and fine particles (< 1 µm) 54.6%-59.1%. Polycyclic aromatic hydrocarbon size distributions in haze periods peaked at 0.75 µm and the concentrations are 2-30 times higher than the normal period. High molecular weight (4-6 ring) PAHs during the haze episode contribute to about 56.7%-88.0% for nanoparticles. The average values of benzo(a)pyrene toxic equivalency quotient were 3.34±2.54ng/m³ in the 2015 haze period but only 0.89±0.17 ng/m³ in 2017. It is clear that particles smaller than 1 µm, were highly toxic. Nanoparticles contributed 19.4%-26.0% of total BaP-TEQ, whereas the mass fraction is 13.1%-14.8%. Thus the nanoparticles were more carcinogenic and can cause greater health effect than larger particles. The fraction of BaP-TEQ for nanoparticles during 2017 non-haze period was nearly the same, while the mass fraction was lower. This indicates that nanoparticles are the significant source of carcinogenic aerosols both during haze and non-haze periods.     

中式餐饮业油烟中非甲烷碳氢化合物排放特征研究

使用挥发性有机物采样标准方法TO-14/15,选择了北京市5家不同菜系、不同营业规模的餐馆,在其营业时段,连续采集油烟中非甲烷碳氢（NMHCs）样品,使用气相色谱质谱联用仪（GC/MS）进行样品分析.研究了4大类72种NMHCs排放浓度和组分组成特点.不同采样餐馆的NMHCs排放浓度存在差异,与菜系类型、规模、上座率、...     

高效液相色谱法测定矿区塌陷区水体中多环芳烃

高效液相色谱法是目前多环芳烃(PAHs)测定最常用技术之一。针对EPA规定的16种优先控制PAHs污染物,采用高效液相色谱法进行矿区塌陷区水体样品的测试。通过紫外-荧光串联使用,紫外检测器变波扫描,荧光检测器波长切换,合理设定流动相梯度洗脱程序等手段优化分析条件,使16个组分在40min内获得良好的分离效果。并分别选取在紫外和荧光检测条件下各组分的最大响应进行定量,使各组分均具有更低的检出限。本方法精密度为0.98%～10.4%,加标回收率达72.4%～112%,可作为各种环境样品中PAHs分析检测的参考。     

Distribution of polycyclic aromatic hydrocarbons in Datuo karst Tiankeng of South China

Levels of polycyclic aromatic hydrocarbons (PAHs) were measured in surface soils of Datuo karst Tiankeng (large sinkholes) in South China with the use of a gas chromatography-mass spectroscopy (GC-MS) system. This paper provides data on the levels and distribution of PAHs from the top to the bottom of the Datuo karst Tiankeng. The results showed that the sum of the 16 EPA priority PAHs from the sampled locations from top to bottom had a relative increment in PAHs concentration. summation operatorPAHs ranged from 16.93 ng/g to 68.07 ng/g with a mean concentration of 42.15 ng/g. The correlated results showed the bottom of the large sinkhole, which accounts for the higher concentrations, probably acts like a trap for the PAHs. Thus, the low evaporation rate at the bottom may play a key role in controlling the high concentration of PAHs at the bottom.     

Investigation of the sources of aliphatic hydrocarbons in the mussel Mytilus edulis from north sea oil production platforms by Capillary glc and CGCMS†

Aliphatic hydrocarbons isolated from mussels collected over a 20 month period from three North Sea Forties field oil production platforms have been examined by capillary gas chromatography and gas chromatography‐mass spectrometry.

The biological hydrocarbons consist predominantly (300–700 μh g^‐1 lipid) of C₃₁ and C₃₃ n‐alkenes with 2, 3 and 4 double bonds probably derived from a dietary intake of Emiliania huxleyi, a microscopic coccolithophorid alga. In some of the mussels C₁₈, C₂₀ and C₂₂ n‐alkanes are present in unusually high abundance compared to their odd carbon number homologues. Possible reasons for this distribution are discussed.

The concentrations of fossil fuel hydrocarbons (mainly unresolved complex mixtures) in the mussels ranged from 330 to 5,298 μg g^‐1 of lipid. No significant increase in values was detected two months after the start of discharge of treated Forties production water from the Forties D platform.

To determine the pollutant hydrocarbon sources, the sterane and terpane distributions of hydrocarbon fractions isolated from the mussels and from a number of fossil fuels, including Forties crude oil, were examined by mass fragmentography. The steranes in the mussels from the Forties C and D platforms contained higher proportions of regular 14α(H), 17α(H) components than Forties oil in which the steranes were mainly 13ß(H), 17α(H) diasteranes. In addition, the terpane distributions of the mussel fractions differed markedly from that of Forties crude oil, particularly in the relative abundance of diterpanes to triterpanes, which was higher in the mussel fractions than in the oil, and in the absence of 17α(H), 18α(H), 21ß(H)‐18, 30‐bisnorhopane, a known component of Forties crude. Furthermore, the ratio of C₂₉ to C₃₀ triterpanes was greater than unity in the mussels but much less than unity in the Forties oil. These data preclude Forties or other similar North Sea crudes as the major source of pollutant aliphatic hydrocarbons in the mussels. The relative concentrations and distributions of steranes and triterpanes suggest that the most likely source of pollutants is a Middle Eastern based oil derived either from rig activities, or from background pollution in the North Sea. The low concentration of ≥ C₂₇ steranes in the more polluted mussels (e.g. Forties B; UCM > 200 ppm dry wt.) suggests that gas oils used on the platforms may be the major source of petrogenic hydrocarbons in these samples.     

How does the brown mussel Perna perna respond to environmental pollution? A review on pollution biomarkers

The brown mussel Perna perna (Linnaeus, 1758) is a valuable resource for aquaculture in tropical and subtropical coastal regions. It presents desirable characteristics for biomonitoring, including being sessile, widely distributed and abundant, and is a filter-feeder able to accumulate several classes of pollutants (e.g., metals, hydrocarbons, among others). Mussels’ biological responses to pollution exposure can be measured as biomarkers, which include alterations ranging from molecular to physiological levels, to estimate the degree of environmental contamination and its effects on biota. This full review compiles two decades (2000–2020) of literature concerning biological effects on P. perna mussel caused by environmental pollutants (i.e., metals, hydrocarbons, and emerging pollutants), considering environmental and farm-based biomonitoring. Biochemical markers related to mussels’ oxidative status were efficient for the biomonitoring of metals (i.e., antioxidant enzymes associated with oxidative damage in biomolecules). Genotoxicity and cytotoxicity indicators (i.e., comet, micronucleus, and neutral red assays) provided a depiction of hydrocarbon contamination. The neutral red assay gave a time-concentration cytotoxic response to a wide range of pollutants, including emerging pollutants (e.g., pharmaceuticals and biocides) and hydrocarbons. Perna perna hemocyte parameters provided a useful approach for biocide biomonitoring. This paper summarizes useful biomarkers from molecular to physiological levels in this mussel species used to identify and quantify the degree of coastal pollution. An integrated biomarker analysis may provide a way to overcome possible biomarker variations and assess multi-polluted sites. Nevertheless, it is necessary to investigate biomarker variations according to natural factors (e.g., season and gonad maturation stage) to standardize them for trustworthy biomonitoring.