Solubility of organic acids in various methanol and salt concentrations: the implication on organic acid sorption in a cosolvent system

The well-known cosolvency-induced sorption model is not applicable to predict the sorption of carboxylic acids in cosolvent system. To investigate the phenomenon, sorption and solubility of chlorinated phenols (2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP)) and carboxylic acids (benzoic acid and 2,4-dichlorophenoxyacetic acid (2,4-D)) were measured in soil-methanol mixture with various ionic strengths. The sorption (K_m) of chlorinated phenols was explained by a cosolvency-induced sorption model; the inverse log-linear relationship between the K_m and methanol volume fraction (f_c). However, the K_m of carboxylic acids increased with increasing f_c. This discrepancy was attributed to the effect of the carboxylic moiety. To explain the effect, solubility was measured for benzoic acid and 2,4,6-TCP from various liquid conditions. For both solutes, the cosolvency power (σ) increased with CaCl₂ concentrations and the salting constant (K^s) became smaller as f_c increased. However, the σ value at a given salt concentration and the K^s value at a given f_c were greater for 2,4,6-TCP than for benzoic acid, both of which were due to the greater hydrophobicity of the former. Overall, the solubility profiles of the both solutes on combination of f_c and CaCl₂ concentration evidenced no specific role of the carboxylic moiety. Therefore, it can be reasonably concluded that the positive relationship between K_m and f_c for carboxylic organic acid can be attributed to the modification of the activity coefficient occurred in the solid phase, which cannot be traceable by cosolvency-based model.     

含多聚甲醛类化合物高浓度COD废水处理方法研究

目标废水来自郴州某制药厂,具有COD高、可生化处理能力差的特点。本实验针对废水特点,提出了Fenton氧化、次氯酸钠氧化等高级氧化为主,活性炭吸附为辅的处理方案,同时探讨了加热回流时间、pH、Fe2＋投加量、H2O2投加量、次氯酸钠投加量分别对COD降解率的影响,得出最佳处理条件。     

Potential of BAC combined with UVC/H2O2 for reducing organic matter from highly saline reverse osmosis concentrate produced from municipal wastewater reclamation

The organic matter present in the concentrate streams generated from reverse osmosis (RO) based municipal wastewater reclamation processes poses environmental and health risks on its disposal to the receiving environment (e.g., estuaries, bays). The potential of a biological activated carbon (BAC) process combined with pre-oxidation using a UVC/H₂O₂ advanced oxidation process for treating a high salinity (TDS ∼ 10 000 mg L⁻¹) municipal wastewater RO concentrate (ROC) was evaluated at lab scale during 90 d of operation. The combined treatment reduced the UVA₂₅₄ and colour of the ROC to below those for the influent of the RO process (i.e., biologically treated secondary effluent), and the reductions in DOC and COD were approximately 60% and 50%, respectively. UVC/H₂O₂ was demonstrated to be an effective means of converting the recalcitrant organic compounds in the ROC into biodegradable substances which were readily removed by the BAC process, leading to a synergistic effect of the combined treatment in degrading the organic matter. The tests using various BAC feed concentrations suggested that the biological treatment was robust and consistent for treating the high salinity ROC. Using Microtox analysis no toxicity was detected for the ROC after the combined treatment, and the trihalomethane formation potential was reduced from 3.5 to 2.8 mg L⁻¹.     

Microwave Pretreatment for Enhancement of Phosphorus Release from Dairy Manure

Both the advanced oxidation process (AOP) using a combination of hydrogen peroxide addition and microwave heating (H₂O₂/microwave), and the microwave heating process were used for solubilization of phosphorus from liquid dairy manure. About 80% of total phosphate was released into the solution at a microwave heating time of 5 min at 170°C. With an addition of H₂O₂, more than 81% of total phosphate could be released over a reaction period of 49 h at ambient temperature. The AOP process could achieve up to 85% of total phosphate release at 120°C. The results indicated that both the microwave, and the AOP processes could effectively release phosphate from liquid dairy manure. These processes could serve as pretreatments for phosphorus recovery from animal wastes, and could be combined with the struvite crystallization process to provide a new approach in treating animal wastes.     

Influence of Substrate on Bioaccumulation of 14C-Paraquat in Compost Worms Eisenia foetida

Contamination of soil with pesticides can be evaluated using toxicity tests with worms because their ecological niche makes them good bioindicators. Bioaccumulation in compost worms of [methyl- ¹⁴C] paraquat (1,1′-dimethyl-4,4′-bipyridinium dichloride) was measured after three-month exposure in two substrates with differing physicochemical characteristics, in particular their organic matter and clay contents. The treatments were 1.2, 12, and 120 μg paraquat g^?1 substrate. The action of the worms did not influence the loss of ¹⁴C from the substrates, as the ¹⁴C-recovered was essentially quantitative at the end of the study in both the presence and absence of the worms. The organic matter and clay contents of the substrates determined the extent of the paraquat uptake by the worms; worms from the substrate with smaller amounts of clay and organic matter had the higher values of the bioconcentration factor (BCF), these being about 5 (fresh-weight basis) and independent of the application rate. The BCF values in the substrate containing more organic matter and clay were smaller but increased from 1.1 to 3.8 with the increasing rates of application. However, in both substrates the amounts of paraquat bioaccumulated in the worms was always less than 1% of that applied, indicating the very strong binding of paraquat to the substrates and hence low availability to the worms.     

Treatment of dairy manure using the microwave enhanced advanced oxidation process under a continuous mode operation

The microwave enhanced advanced oxidation process (MW/H₂O₂-AOP) was used to treat dairy manure for solubilization of nutrients and organic matters. This study investigated the effectiveness of the MW/H₂O₂-AOP under a continuous mode of operation, and compared the results to those of batch operations. The main factors affecting solubilization by the MW/H₂O₂-AOP were heating temperature and hydrogen peroxide dosage. Soluble chemical oxygen demand (SCOD) and volatile fatty acids (VFA) increased with an increase of microwave (MW) heating temperature; very high concentrations were obtained at 90°C. Insignificant amounts of ammonia and reducing sugars were released in all runs. An acidic pH condition was required for phosphorus solubilisation from dairy manure. The best yield was obtained at 90°C with an acid dosage of 1.0 %; about 92 % of total phosphorus and 90 % of total chemical oxygen demand were in the soluble forms. The MW/H₂O₂-AOP operated in a continuous operation mode showed pronounced synergistic effects between hydrogen peroxide and microwave irradiation when compared to a batch system under similar operating conditions, resulting in much better yields.     

Measuring and modeling nitrous oxide and methane emissions from beef cattle feedlot manure management: First assessments under Brazilian condition

Intensive beef production has increased during recent decades in Brazil and may substantially increase both methane (CH₄) and nitrous oxide (N₂O) emissions from manure management. However, the quantification of these gases and methods for extrapolating them are scarce in Brazil. A case study examines CH₄ and N₂O emissions from one typical beef cattle feedlot manure management continuum in Brazil and the applicability of Manure-DNDC model in predicting these emissions for better understand fluxes and mitigation options. Measurements track CH₄ and N₂O emissions from manure excreted in one housing floor holding 21 animals for 78 days, stockpiled for 73 days and field spread (360 kg N ha^?1). We found total emissions (CH₄ + N₂O) of 0.19 ± 0.10 kg CO₂eq per kg of animal live weight gain; mostly coming from field application (73%), followed housing (25%) and storage (2%). The Manure-DNDC simulations were generally within the statistical deviation ranges of the field data, differing in ?28% in total emission. Large uncertainties in measurements showed the model was more accurate estimating the magnitude of gases emissions than replicate results at daily basis. Modeled results suggested increasing the frequency of manure removal from housing, splitting the field application and adopting no-tillage system is the most efficient management for reducing emissions from manure (up to about 75%). Since this work consists in the first assessment under Brazilian conditions, more and continuous field measurements are required for decreasing uncertainties and improving model validations. However, this paper reports promising results and scientific perceptions for the design of further integrated work on farm-scale measurements and Manure-DNDC model development for Brazilian conditions.     

Bioenergy production from diluted poultry manure and microbial consortium inside Anaerobic Sludge Bed Reactor at sub-mesophilic conditions

In this study, anaerobic treatability of diluted chicken manure (with an influent feed ratio of 1 kg of fresh chicken manure to 6 L of tap water) was investigated in a lab-scale anaerobic sludge bed (ASB) reactor inoculated with granular seed sludge. The ASB reactor was operated at ambient temperature (17–25°C) in order to avoid the need of external heating up to higher operating temperatures (e.g., up to 35°C for mesophilic digestion). Since heat requirement for raising the temperature of incoming feed for digestion is eliminated, energy recovery from anaerobic treatment of chicken manure could be realized with less operating costs. Average biogas production rates were calculated ca. 210 and 242 L per kg of organic matter removed from the ASB reactor at average hydraulic retention times (HRTs) of 13 and 8.6 days, respectively. Moreover, average chemical oxygen demand (COD) removal of ca. 89% was observed with suspended solids removal more than 97% from the effluent of the ASB reactor. Influent ammonia, on the other hand, did not indicate any free ammonia inhibition due to dilution of the raw manure while pH and alkalinity results showed stability during the study. Microbial quantification results indicated that as the number of bacterial community decreased, the amount of Archaea increased through the effective digestion volume of the ASB reactor. Moreover, the number of methanogens displayed an uptrend like archaeal community and a strong correlation (?0.645) was found between methanogenic community and volatile fatty acid (VFA) concentration especially acetate.     

Assessment of a composting process for the treatment of beef cattle manure

The intensive breeding of beef cattle in Juncosa de les Garrigues (Catalonia, Spain) leads to the production of a large volume of manure that needs appropriate management. Land application in the area at agronomic rates is not enough to ensure good management practices, making necessary extended on-farm storage and the export of part of the production to long distances. In this context, the implementation of a collective treatment based on composting could help in enhancing the handling of manure. We assessed a full-scale composting process based on turned windrows (W), and involving treatment of beef cattle manure (CM) alone (two typologies were considered according to carbon-to-nitrogen ratios of ~25 (CM1, W1) and ~14 (CM2, W2)), or mixed with bulking agent (CM2/BA, W3) and dewatered digested sewage sludge (CM2/BA/DDSS, W4). Composting significantly improved the transportability of nutrients (final volumes were 40–54% of the initial volume). Temperature >55°C was reached in all the treatments but following different time patterns. Under the applied conditions of turning and rewetting, 14 weeks of processing did not ensure the production of stable, and mature, compost. Thus, only compost from W1 attained the maximum degree of stability as well as concentration of ammonium–N < 0.01% (with ammonium–N/nitrate–N ratio of 0.2) and low phytotoxicity. However, high pH, salinity, and heavy metal contents (Cu and Zn) may limit its final use. Addition of BA was advised to be kept to minimum, whereas use of DDSS as a co-substrate was not recommended in agreement to the higher loss of N and levels of heavy metals in the final compost.