5:3 Polyfluorinated acid aerobic biotransformation in activated sludge via novel "one-carbon removal pathways"

The polyfluorinated carboxylic acids 5:3 acid (C₅F₁₁CH₂CH₂CO₂H) and 7:3 acid (C₇F₁₅CH₂CH₂CO₂H) are major products from 6:2 FTOH (C₆F₁₃CH₂CH₂OH) and 8:2 FTOH (C₈F₁₇CH₂CH₂OH) aerobic biotransformation, respectively. The 5:3 and 7:3 acids were dosed into domestic WWTP activated sludge for 90 d to determine their biodegradability. The 7:3 acid aerobic biodegradability was low, only 1.7 mol% conversion to perfluoroheptanoic acid (PFHpA), whereas no transformation was observed previously in soil. In stark contrast, 5:3 acid aerobic biodegradability was enhanced 10 times in activated sludge compared to soil. The 5:3 acid was not activated by acyl CoEnzyme A (CoA) synthetase, a key step required for further α- or ß-oxidation. Instead, 5:3 acid was directly converted to 4:3 acid (C₄F₉CH₂CH₂CO₂H, 14.2 mol%) and 3:3 acid (C₃F₇CH₂CH₂CO₂H, 0.9 mol%) via “one-carbon removal pathways”. The 5:3 acid biotransformation also yielded perfluoropentanoic acid (PFPeA, 5.9 mol%) and perfluorobutanoic acid (PFBA, 0.8 mol%). This is the first report to identify key biotransformation intermediates which demonstrate novel one-carbon removal pathways with sequential removal of CF₂ groups. Identified biotransformation intermediates (10.2 mol% in sum) were 5:3 Uacid, α-OH 5:3 acid, 5:2 acid, and 5:2 Uacid. The 5:2 Uacid and 5:2 acid are novel intermediates identified for the first time which confirm the proposed pathways. In the biodegradation pathways, the genesis of the one carbon removal is CO₂ elimination from α-OH 5:3 acid. These results suggest that there are enzymatic mechanisms available in the environment that can lead to 6:2 FTOH and 5:3 acid mineralization. The dehydrogenation from 5:3 acid to 5:3 Uacid was the rate-limiting enzymatic step for 5:3 acid conversion to 4:3 acid.     

The effect of copper ions on the lipid composition of subcellular membranes in Hydrilla verticillata

The paper studies changes in the content and composition of lipids in the membranes of chloroplasts, mitochondria and microsomes of the aquatic plant Hydrilla verticillata exposed to copper ions (100 μM; 1, 3, 6 and 24 h). The rate of copper accumulation and the coefficient of its extraction by the plant were also determined. The presence of copper in the incubation medium and its accumulation in the plant tissues decreased the content of photosynthetic pigments, stimulated lipid peroxidation and enhanced membrane permeability. The gradual accumulation of copper in the plant tissues was accompanied by specific changes in the composition of lipids: the content of sulfolipids (SQDG) in chloroplasts declined; the content of monogalactosyl diacylglycerols (MGDG), digalactosyl diacylglycerols (DGDG) and phosphatidyl glycerols (PG) in chloroplasts and mitochondria grew after an hour of copper exposure; and the content of all the lipids except phosphatidic acids (PA) decreased after 3 h of exposure. The decline in the content of phosphatidyl cholines (PC) was first observed in the membranes of microsomes (after an hour of exposure) and later in the membranes of chloroplasts and mitochondria (after 3-6 h of exposure). The experiments with incorporation of [2-¹⁴C]sodium acetate into fatty acids of polar lipids showed that in parallel with lipid destruction, there took place an intensive and specific renewal of the lipid pool of subcellular membrane fractions.     

Early changes in the fatty acid composition of photosynthetic membrane lipids from Populus nigra grown on a metallurgical landfill

We compared the fatty acid composition of leaves taken from poplars on a metal-contaminated landfill, and on the uncontaminated roadside bordering this site. For the first time, it is shown that the percentage of linolenic acid, which is mainly associated with thylakoid lipids, was significantly lower in tree species within the landfill than within the control area. A correlation study was carried out to investigate relationships between the C18:3/(C18:0 + C18:1 + C18:2) fatty acid ratios and the metal contents in soils and leaves. Lead and chromium leaf contents were significantly negatively correlated to this fatty acid ratio. The impact of each of these metals remains difficult to evaluate, but chromium in leaf likely plays a major role in toxicity. In addition, the decrease in the C18:3/(C18:0 + C18:1 + C18:2) fatty acid ratio occurred at low leaf metal content, and therefore it is shown that this ratio can be used as an early indicator of the effect of metals.     

Volatile organic compounds at swine facilities: A critical review

Volatile organic compounds (VOCs) are regulated aerial pollutants that have environmental and health concerns. Swine operations produce and emit a complex mixture of VOCs with a wide range of molecular weights and a variety of physicochemical properties. Significant progress has been made in this area since the first experiment on VOCs at a swine facility in the early 1960s. A total of 47 research institutions in 15 North American, European, and Asian countries contributed to an increasing number of scientific publications. Nearly half of the research papers were published by U.S. institutions.Investigated major VOC sources included air inside swine barns, in headspaces of manure storages and composts, in open atmosphere above swine wastewater, and surrounding swine farms. They also included liquid swine manure and wastewater, and dusts inside and outside swine barns. Most of the sample analyses have been focusing on identification of VOC compounds and their relationship with odors. More than 500 VOCs have been identified. About 60% and 10% of the studies contributed to the quantification of VOC concentrations and emissions, respectively. The largest numbers of VOC compounds with reported concentrations in a single experimental study were 82 in air, 36 in manure, and 34 in dust samples.The relatively abundant VOC compounds that were quantified in at least two independent studies included acetic acid, butanoic acid (butyric acid), dimethyl disulfide, dimethyl sulfide, iso-valeric, p-cresol, propionic acid, skatole, trimethyl amine, and valeric acid in air. They included acetic acid, p-cresol, iso-butyric acid, butyric acid, indole, phenol, propionic acid, iso-valeric acid, and skatole in manure. In dust samples, they were acetic acid, propionic acid, butyric acid, valeric acid, p-cresol, hexanal, and decanal. Swine facility VOCs were preferentially bound to smaller-size dusts.Identification and quantification of VOCs were restricted by using instruments based on gas Chromatography (GC) and liquid chromatography (LC) with different detectors most of which require time-consuming procedures to obtain results. Various methodologies and technologies in sampling, sample preparation, and sample analysis have been used. Only four publications reported using GC based analyzers and PTR-MS (proton-transfer-reaction mass spectrometry) that allowed continuous VOC measurement. Because of this, the majority of experimental studies were only performed on limited numbers of air, manure, or dust samples. Many aerial VOCs had concentrations that were too low to be identified by the GC peaks.Although VOCs emitted from swine facilities have environmental concerns, only a few studies investigated VOC emission rates, which ranged from 3.0 to 176.5 mg d⁻¹ kg⁻¹ pig at swine finishing barns and from 2.3 to 45.2 g d⁻¹ m⁻² at manure storages. Similar to the other pollutants, spatial and temporal variations of aerial VOC concentrations and emissions existed and were significantly affected by manure management systems, barn structural designs, and ventilation rates.Scientific research in this area has been mainly driven by odor nuisance, instead of environment or health concerns. Compared with other aerial pollutants in animal agriculture, the current scientific knowledge about VOCs at swine facilities is still very limited and far from sufficient to develop reliable emission factors.     

Application of an early warning indicator and CaO to maximize the time–space-yield of an completely mixed waste digester using rape seed oil as co-substrate

In order to increase the organic loading rate (OLR) and hereby the performance of biogas plants an early warning indicator (EWI-VFA/Ca) was applied in a laboratory-scale biogas digester to control process stability and to steer additive dosing. As soon as the EWI-VFA/Ca indicated the change from stable to instable process conditions, calcium oxide was charged as a countermeasure to raise the pH and to bind long-chain fatty acids (LCFAs) by formation of aggregates. An interval of eight days between two increases of the OLR, which corresponded to 38% of the hydraulic residence time (HRT), was sufficient for process adaptation. An OLR increase by a factor of three within six weeks was successfully used for biogas production. The OLR was increased to 9.5 kg volatile solids (VS) m^?3 d^?1 with up to 87% of fat. The high loading rates affected neither the microbial community negatively nor the biogas production process. Despite the increase of the organic load to high rates, methane production yielded almost its optimum, amounting to 0.9 m³ (kg VS)^?1. Beneath several uncharacterized members of the phylum Firmicutes mostly belonging to the family Clostridiaceae, a Syntrophomonas-like organism was identified that is known to live in a syntrophic relationship to methanogenic archaea. Within the methanogenic group, microorganisms affiliated to Methanosarcina, Methanoculleus and Methanobacterium dominated the community.     

Recovery of volatile fatty acids via membrane contactor using flat membranes: Experimental and theoretical analysis

Volatile fatty acid (VFA) separation from synthetic VFA solutions and leachate was investigated via the use of a membrane contactor. NaOH was used as a stripping solution to provide constant concentration gradient of VFAs in both sides of a membrane. Mass flux (12.23 g/m² h) and selectivity (1.599) observed for acetic acid were significantly higher than those reported in the literature and were observed at feed pH of 3.0, flow rate of 31.5 ± 0.9 mL/min, and stripping solution concentration of 1.0 N. This study revealed that the flow rate, stripping solution strength, and feed pH affect the mass transfer of VFAs through the PTFE membrane. Acetic and propionic acid separation performances observed in the present study provided a cost effective and environmental alternative due to elimination of the use of extractants.     

Long-term thermophilic mono-digestion of rendering wastes and co-digestion with potato pulp

In this study, mono-digestion of rendering wastes and co-digestion of rendering wastes with potato pulp were studied for the first time in continuous stirred tank reactor (CSTR) experiments at 55 °C. Rendering wastes have high protein and lipid contents and are considered good substrates for methane production. However, accumulation of digestion intermediate products viz., volatile fatty acids (VFAs), long chain fatty acids (LCFAs) and ammonia nitrogen (NH₄-N and/or free NH₃) can cause process imbalance during the digestion. Mono-digestion of rendering wastes at an organic loading rate (OLR) of 1.5 kg volatile solids (VS)/m³ d and hydraulic retention time (HRT) of 50 d was unstable and resulted in methane yields of 450 dm³/kg VS_fed. On the other hand, co-digestion of rendering wastes with potato pulp (60% wet weight, WW) at the same OLR and HRT improved the process stability and increased methane yields (500–680 dm³/kg VS_fed). Thus, it can be concluded that co-digestion of rendering wastes with potato pulp could improve the process stability and methane yields from these difficult to treat industrial waste materials.     

湿热处理餐厨废弃物不饱和脂肪酸

为了研究湿热水解技术对餐厨废弃物中脂类物质的影响,促进餐厨废弃物的资源化处理利用,通过实验研究,分析了餐厨废弃物固相中油酸、亚油酸、α-亚麻酸和花生四烯酸4种不饱和脂肪酸在90～140℃湿热条件下处理随时间的变化规律。结果表明：实验所取餐厨废弃物经湿热处理后固相中油酸和亚油酸的含量相对较高,约为30％,花生四烯酸的含量较低,约为0．3％,随着加热时间延长,亚油酸在湿热环境下发生化学分解,其含量不断降低,而花生四烯酸的含量显著增加。当加热温度为100～120℃,加热时间为30-60min时,餐厨废弃物脂类含量比较稳定,作为适宜的湿热处理条件。值得注意的是,湿热处理后的餐厨废弃物中花生四烯酸的含量只约为0．3％,不能满足饲料标准中2％的要求。     

再生水中消毒副产物——卤乙酸的测定方法研究

参照美国国家环保局(USEPA)推荐的饮用水卤乙酸类消毒副产物测定方法(Method 552.3),通过优化该方法的预处理条件和改变检测方法,提出了酸化萃取-衍生化-中和萃取-GC-MS测定再生水中卤乙酸含量的分析方法,并分析了北方某市再生水中4种卤乙酸类消毒副产物含量。结果表明,该方法适用于我国再生水水质,能够有效地消除再生水中共存污染物的干扰;其相对标准偏差(n=7)小于10%,方法的精密度较好;检出限与USEPA方法基本一致;样品加标回收率满足USEPA 6251B标准方法中(100±30)%要求;再生水中的卤乙酸比自来水高出几十倍,对环境和人类存在一定的潜在危害。     

餐厨垃圾单相厌氧酸化系统恢复参数

针对现今餐厨垃圾单相厌氧酸化系统缺乏有效的恢复性监控指标,提出可有效表征酸化系统恢复的监控指标。在中温条件下,连续对餐厨垃圾单相厌氧消化系统进行负荷冲击及恢复,分别对p H、沼气产率及成分、挥发性脂肪酸组成成分、总碱度(TA)和碳酸氢盐碱度(BA)及其组合指标进行监测分析。结果表明,传统单因子参数不能有效地指示系统恢复,选取VFA/BA和丙酸/乙酸的比值作为餐厨垃圾单相厌氧酸化系统恢复指示性参数。在酸化系统恢复过程中,当丙酸/乙酸≤1.4、VFA/BA≤0.4时,表明系统中各种挥发酸浓度值已恢复正常,且具有足够的缓冲能力,可提高反应器负荷,保证反应器恢复启动运行。