An alternative supercritical fluid extraction system for aqueous matrices and its application in pesticides residue analysis

Supercritical fluid extraction (SFE) is a rapid and convenient method for the isolation of organic compounds from environmental samples. This paper describes a supercritical carbon dioxide (CO2) extraction system that uses a newly designed extraction cell to recover organic compounds from an aqueous matrix. Analysis of the extracts by gas chromatography-electron capture detector (GC-ECD) indicated that the herbicide trifluralin (2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline) could be quantitatively extracted by using the SFE system proposed with small amounts of sample. The percentage of recovery obtained with the SFE system described was twice as high as the result obtained using a conventional solid-phase extraction technique. Extraction by SFE was completed in a short period of time using a simple and low-cost home-made system that did not require the use of organic solvents.     

Evaluation of C18 solid‐phase extraction cartridges for the isolation of select pesticides and metabolites

Abstract

Nine different C₁₈ solid‐phase extraction (SPE) cartridges were evaluated for their efficiency at extracting nine pesticides and two s‐triazine metabolites from spiked deionized water samples. The SPE cartridges were found to contain nitrogen (N) and/or phosphorus (P) contaminants and varied in their extraction efficiency for certain pesticides and metabolites. Four of the nine SPE cartridges gave acceptable (70 to 120%) pesticide and metabolite recovery percentages, while five cartridges had marginal (50 to 70%) to poor (< 50%) recoveries. Statistical analyses showed that the poor to marginal recoveries found for three compounds could not be explained by considering several indigenous chemical and physical traits of the cartridge. It is suggested that proper SPE cartridge selection for pesticide recovery should be evaluated using several different cartridges.     

Swine wastewater treatment in a two stage sequencing batch reactor using real‐time control

Abstract

A laboratory scale two‐stage sequencing batch reactor (TSSBR) was used to study the effectiveness of pH as a real‐time control parameter in swine wastewater treatment. A Ringlace media was inserted into the A/O (Anoxic/Oxic) reactor for bacteria immobilization. The TSSBR was subjected to three levels of organic loading. The pH and ORP (Oxidation Reduction Potential) patterns obtained were consistent with distinct features, enabling the real‐time control strategy to effectively set a flexible aeration time pending on influent concentration, hence resulting in flexible cycle time and HRT (Hydraulic Retention Time) for the system. The real‐time process ensured a removal efficiency of over 99% and 95%, respectively, for ammonia and TOC (Total Organic Carbon). For NO₃ ^‐‐N and PO₄ ^‐3, the run with influent TOC = 4,000 mg/L yielded the most efficient removal of 61% and 95%, respectively. Test results suggest that pH can be a viable tool for on‐line real‐time control of a biological treatment process.     

Feasibility of Soil Dust Source Apportionment by the Pyrolysis-Gas Chromatography/Mass Spectrometry Method

Abstract

This study tested the feasibility of using pyrolysis (Py)-gas chromatography (GC)/mass spectrometry (MS) to obtain organic chemical species data suitable for source apportionment modeling of soil-derived coarse particulate matter (PM₁₀) dust on ambient filters. A laboratory resuspension apparatus was used with known soils to generate simulated receptor filter samples loaded with ～0.4 mg of PM₁₀ dust, which is within the range of mass loading on ambient filters. Py-GC/MS at 740 °C generated five times more resolvable compounds than were obtained with thermal desorption GC/MS at 315 °C. The identified compounds were consistent with literature from Py experiments using larger samples of bulk soils. A subset of 91 organic species out of the 178 identified Py products was used as input to CMB8 software in a demonstration of source apportionment using laboratory-generated mixtures simulating ambient filter samples. The 178 quantified organic species obtained by Py of soil samples is an improvement compared with the 38 organic species obtained by thermal desorption of soils and the four functionally defined organic fractions reported by thermal/optical reflectance. Significant differences in the concentration of specific species were seen between samples from different sites, both geographically distant and close, using analysis of variance and cluster analysis. This feasibility study showed that Py-GC/MS can generate useful source profile data for receptor modeling and justifies continued method development.     

Highly efficient recovery of molybdenum from spent catalyst by an optimized process

ABSTRACT

Disposal of spent catalyst in an economical and green way has become a great concern for industrial production. We developed a process including acid leaching, solvent extraction and stripping in order to recycle spent catalyst. In this study, we conducted selective recovery of molybdenum through focus on finding an optimized extraction and stripping process by comparing different extractants and stripping agents. To separate molybdenum from other metals efficiently and figure out the mechanism of extraction process, the five different extractants of methyl trioctyl ammonium chloride, tri-n-octylamine, tris (2-ethylhexyl) amine, bis (2-ethylhexyl) phosphate, and tributyl phosphate with different functional groups were examined; the extraction ability and extraction mechanism of these five extractants were systematically studied under the same system for the first time. It was found that more than 98% of the molybdenum could be extracted with an organic phase consisting of tri-n-octylamine or methyl trioctyl ammonium chloride under the optimal conditions. The result indicated that the tri-n-octylamine and methyl trioctyl ammonium chloride possess excellent molybdenum extraction ability, the extraction capacity of the rest extractants was in the order of bis (2-ethylhexyl) phosphate > tris (2-ethylhexyl) amine > tributyl phosphate. In the stripping process, NH₄OH, NaOH, and H₂SO₄ were chosen as stripping agent to strip the molybdenum from the loaded tri-n-octylamine organic phase. The stripping ability of the three studied stripping agents was in the order NaOH > NH₄OH > H₂SO₄. The Fourier transform infrared (FTIR) spectra showed that the structure of the tri-n-octylamine organic phase was stable during the extraction and stripping process. Results showed that molybdenum could be highly and efficiently recovered by optimized extraction and stripping process.

Implications: A series of different extractants and stripping agent have been systematically studied in order to compare their extraction and stripping ability under the same system. Based on the obtained results, an optimized extraction and stripping process was proposed to recycle molybdenum from spent catalyst efficiently. It is possible to dispose spent catalysts in an economic and environmental way by this developed metal recovery process.     

Nitrification/denitrification in an intermittent aeration process for swine wastewater

Abstract

Nitrogen removal by a methane fermentation plus activated sludge process with the intermittent aeration was presented based upon a full‐scale pig farm experiment. Swine wastewater had a T‐N/BOD ratio from 0.2–0.29. The BOD concentration input to the process ranged from 1050–1608 mg l^‐1 and the T‐N concentration from 273–350 mg l^‐1. More than 90% of organic carbon was removed in each experimental run. Only small concentrations of NO₃‐N were found in the effluent and higher than 60% of the T‐N and 73% of NH₄‐N which were loaded to the intermittent aeration tank was removed. The nitrogen balance of each run was calculated. Denitrification was estimated to be accountable for 45–90% of the T‐N removed in the intermittent aeration tank. Denitrification rate increased as the BOD concentration increased (> 1300 mg l^‐1). The T‐N removal percentage was a function of the T‐N/BOD ratio of the influent. Although higher DO concentration (> 3 mg l^‐1) did not enhance the denitrification rate, nitrification did maintain at relative higher rates at a lower DO concentration (ave. 1.5 mg l^‐1). An operational condition of intermittent interval of aeration/nonaeration at 1:1 hr is better than that of the condition at 3:1 hr. As a result, T‐N and NH4‐N were removed up to 30% and 40% respectively, and the denitrification rate reached 79% in the intermittent aeration tank. An experimental run in a pilot plant on treating anaerobically pretreated swine wastewater was observed to verify simultaneous nitrification/denitrification. The results of the full‐scale plant experimentation seem to be confirmed by those obtained from the pilot plant runs.     

Pesticide concentration variations correlated with well bore volume removal in shallow coastal plain ground water

Abstract

The effects of well bore volume removal (V_n) on the concentration of alachlor [2‐chloro‐N‐(2,6‐diethylphenyl)‐N‐(methoxy methyl) acetamide] and prometon (6‐methoxy‐N,N'‐bis(1‐methylethyl)‐1,3,5‐triazine‐2,4‐diamine] in ground water obtained from three monitoring wells installed in the Coastal Plain region of North Carolina was investigated. Seasonal effects were also investigated by conducting the exercise in February and May. In the majority of cases, the lowest pesticide concentrations occurred in the initial well bore volume (V₁ = stagnant water). Removal of additional well bore volumes (V₂ to V₁₀) from two of the wells resulted in pesticide concentrations that did not vary substantially. This indicates that a representative aquifer sample was obtainable, in most cases from these wells, after removal of the initial well bore volume. In contrast, a third well required the purging of two well bore volumes before a stable alachlor concentration was achieved. Seasonal effects of bore volume removal vs. pesticide concentrations for the three wells were not significant (P > 0.05). It was concluded that a protocol for improved accuracy in pesticide analyses of ground water can be obtained by establishing a pesticide concentration‐purging (well bore volume) relationship for each well.     

Monitoring of pesticide residues in a cotton crop soil

Abstract

This paper reports on the residues of methyl parathion (O,O‐dimethyl O‐4‐nitrophenyl phosphorothioate), trifluralin (α, α, α‐trifluoro‐2, 6‐dinitro‐N, N‐dipropyl‐p‐toluidine), endosulfan [(1, 4, 5, 6, 7, 7‐hexachloro‐8, 9, 10‐trinorborn‐5‐en‐2, 3‐ylenebismethylene) sulfite] and dimethoate (O, O‐dimethyl S‐methylcarbamoylmethyl phosphorodithioate) in a cotton crop soil. Soil samples (0–15 cm) were collected at different periods from the cotton crop farm and subjected to Soxhlet extraction. The extracted material was analysed after clean‐up by a HP5890 II gas Chromatograph equipped with a ⁶³Ni electron‐capture detector (ECD‐⁶³Ni) and fitted with a 25m x 0,2mm i.d. fused silica capillary column [Ultra‐2 (5% phenylmethyl polysiloxane)]. The recoveries of the pesticide residues from the spiked control soil were determined after Soxhlet extraction and C₁₈ cartridges clean‐up by using radiotracer techniques with the corresponding ¹⁴C‐pesticides. The results show that in the cotton crop soil the pesticide residues under study were present in the range of 0.1 to 0.4 mg ? kg^‐1. Endosulfan was found to be rapidly degraded in the soil and formed a sulfate metabolite.     

An Investigation of Odors and Volatile Organic Compounds Released during Composting

ABSTRACT

The emissions of odors and volatile organic compounds produced from a commercial composting operation have been studied using a laboratory-scale composting system. The composting activity of a typical commercial compost feed was followed by monitoring the composting temperature, as well as the respiratory rate. Using a controlled aeration system, the gaseous volatiles produced were tested for odors using the "dilution-to-threshold" method, as well as gas composition, as determined by gas chromatography-mass spectrometry.

The results indicated that while there may be a reasonable correlation between the release of volatile organic compounds (VOCs) and odors, care has to be taken when trying to identify offensive odors with specific chemical species. However, the data obtained suggests that offensive odors formed during commercial composting may be due to sulfurous and nitrogenous compounds, although their concentrations in the compost gases may not be very high.

The major release of VOCs occurred during the first two weeks of composting, after which the gaseous releases fell dramatically as the composting process proceeded and temperatures started to fall.     

Air Quality Modeling of Interpollutant Trading for Ozone Precursors in an Urban Area

Abstract

Emission trading is a market‐based approach designed to improve the efficiency and economic viability of emission control programs; emission trading has typically been confined to trades among single pollutants. Interpollutant trading (IPT), as described in this work, allows for trades among emissions of different compounds that affect the same air quality end point, in this work, ambient ozone (O₃) concentrations. Because emissions of different compounds impact air quality end points differently, weighting factors or trading ratios (tons of emissions of nitrogen oxides (NO_x) equivalent to a ton of emissions of volatile organic compounds [VOCs]) must be developed to allow for IPT. In this work, IPT indices based on reductions in O₃ concentrations and based on reductions in population exposures to O₃ were developed and evaluated using a three‐dimensional gridded photochemical model for Austin, TX, a city currently on the cusp of nonattainment with the National Ambient Air Quality Standards for O₃ concentrations averaged over 8 hr. Emissions of VOC and NO_x from area and mobile sources in Austin are larger than emissions from point sources. The analysis indicated that mobile and area sources exhibited similar impacts. Trading ratios based on maximum O₃ concentration or population exposure were similar. In contrast, the trading ratios did exhibit significant (more than a factor of two) day‐to‐day variability. Analysis of the air quality modeling indicated that the daily variability in trading ratios could be attributed to daily variations in both emissions and meteorology.     

Nitrogen and phosphorus removal for swine wastewater by ammonium crystallization and intermittent aeration process

Abstract

A process on crystallized precipitation of ammonium by adding magnesium salt and phosphate was carried out to improve C/N ratio in swine wastewater. After completion of crystallized precipitation of ammonium, an intermittent aeration process with aeration and non‐aeration periods alternated at interval of 1:1 hr day^‐1 is used for the improved swine wastewater (T‐N/BOD=0.14: BOD=8200 mg/liter and T‐N=1166 mg/liter). The results obtained from the experiment show that the removal ratios of T‐N and NH₄‐N are 91% and 99%, respectively. T‐P is not removed, while the removal ratio of PO₄‐P is 60% as 3% of CaCl₂ liquid is added. The results also indicate that dilution with water is effective to improve the removal of phosphorus even if raw swine wastewater contains high concentrations of T‐N, T‐P, BOD, and TOC.     

Aged and bound herbicide residues in soil and their bioavailability part 2: Uptake of aged and non‐extractable (bound) [carbonyl‐14C] methabenzthiazuron residues by maize

Abstract

[Carbonyl‐ C]methabenzthiazuron (MBT) was applied to growing winter wheat in an outdoor lysimeter. The amount applied corresponded to 4 kg Tribunil/ha. 140 days after application the 0–2,5 cm soil layer was removed from the lysimeter. This soil contained about 40 % of the applied radioactivity. Using 0,01 M CaCl₂ solution or organic solvents, the extractable residues were removed from the soil. The bioavailability of the non‐extractable as well as aged residues remaining in the soil was investigated in standardized microecosystems containing 1.5 kg of dry soil. During a 4 weeks period the total uptake (4 maize plants/pot) amounted up to 3,6; 2,2; and 0,9 % of the radioactivity from soils containing aged MBT residues, MBT residues non‐extractable‐with 0,01 MCaCl₂ or MBT residues non‐extractable with organic solvents, respectively. About 20 % of the radioactivity found in maize leaves represented chromatographically characterized parent compound. At the end of the plant experiment the soil was extracted again with 0,01 M CaCl₂ and with organic solvents. The soil extracts and also the organic phases obtained from the aqueous fulvic acid solution contained unchanged parent compound.     

Chlorothalonil binding to aquatic humic substances assessed from gas purge studies

Abstract

Fate of the fungicide chlorothalonil (TCIN) binding to dissolved organic acid fractions was quantified using gas‐purge desorption studies. Binding studies were conducted to measure the dissolved organic carbon partition constant (K_DOC) with aquatic fulvic and humic acid fractions purified from cranberry bog water. Desorption studies at DOC concentrations up to 50 mg L^‐1 resulted in mean log K_DOC values of 4.63 (s.d.=0.5, n=8) and 4.81 (s.d.=0.7, n=7) for fulvic and humic acids, respectively. These values deviated from reported K_OC (organic carbon) values by 0.5 to 1.5 orders of magnitude. The relationship between K_OC and K_DOC did not conform to accepted ratios of 10: 1 to 3: 1, although these studies were conducted with the strong hydrophobic fraction of DOC. Binding was rapid suggesting hydrophobic partitioning or weak Van Der Waals forces as binding mechanisms. The strong binding potential for TCIN to aquatic humic substances corresponds to increased solubility in the aqueous system. Sorption to DOC suggests a possible transport mechanism which may result in elevated concentrations of TCIN in cranberry bog systems.     

Using supercritical fluid extraction to measure the desorption and bioaccessibility of phenanthrene in soils

The aim of this paper was to measure the changing desorbable fraction and bioaccessibility of phenanthrene in two different soils with increasing soil-phenanthrene contact time using supercritical fluid extractions (SFE). Both soils were spiked with 100 mg kg⁻¹ phenanthrene and aged for 28 d. Desorption profiles were measured every 7 d using selective SFE conditions and the results were compared to ¹⁴C-phenanthrene mineralisation assays. Selective SFE showed significant differences in the rates and extents of desorption in the two soils, likely to be due to different organic matter composition. Post-extraction fitting of data yielded consistent SFE extraction times within ageing soils for bioaccessibility prediction.     

Extraction of raw sewage sludge containing iron phosphate for phosphorus recovery

The objective of the present study was to establish an alkali extraction technology for FePO₄-containing sewage sludge obtained from a wastewater treatment system that includes phosphorous removal by iron electrolysis. By clarifying the extraction properties of phosphorous, organic matter, and inorganic matter, conditions for alkali extraction were optimized. As a result, it was suggested that unheated phosphorous extraction would be superior for FePO₄-containing sewage sludge. And, extraction methods and sewage sludge properties were also compared, and the noteworthy result that extraction of metals can be suppressed to extremely low amounts with alkali extraction as compared with acid extraction was obtained. A new insight was also gained that, as compared with the use of incinerated ash reported in previous studies, alkali extraction was more efficient when raw sewage sludge was used.     

Biodegradation of Trifluralin in Harran Soil

Abstract

Degradation of trifluralin (α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine) was investigated in soils taken from three different locations at Harran region of Turkey under laboratory conditions. Surface (0–10 cm) soils, which were taken from a pesticide untreated field Gürgelen, Harran-1 and Ikizce regions in the Harran Plain, were incubated in biometer flasks for 350 days at 25°C. Ring-UL-¹⁴C-trifluralin was applied at the rate of 2 µg g^?1 with 78.7 kBq radioactivity per 100 g soil flask. Evolved ¹⁴CO₂ was monitored in KOH traps throughout the experiment. Periodically, soil sub-samples were removed and extracted by supercritical fluid extraction (SFE). Unextractable soil-bound ¹⁴C residues were determined by combustion. During the 350 days incubation period 6.6, 5.4, and 3.3% of the applied radiocarbon was evolved as ¹⁴CO₂ from the Harran-1, Gürgelen, and Ikizce soil, respectively. At the end of 350 days the SFE-extractable and bound ¹⁴C-trifluralin residues were 39.0 and 29.2% of the initially applied herbicide in Gürgelen soil. The corresponding values for Harran-1 and Ikizce soils were 36.2, 28.4% and 41.6, 18.5% respectively.     

Release of soil bound (nonextractable) residues by various physiological groups of microorganisms∗

Abstract

Soil bound ¹⁴C‐labeled residues were released by four different physiological groups of microorganisms from an organic soil treated with ¹⁴C‐ring‐labeled prometryn [2‐(methylthio) ‐4,6‐bis(isopropylamino)‐s‐triazine]. The extent to which the different microbial populations released bound ¹⁴C residues (25–30% of the total bound ¹⁴C) from the Y‐irradiated soil after 28 days incubation did not differ considerably. Analysis of the extractable material from the incubated soil showed the presence of small amounts of the parent compound, and its hydroxy and mono‐N‐dealkylated analogues. Low level of ¹⁴CO₂ (1.5–3.0% of the total bound ¹⁴C) was evolved from the microbial systems indicating ring cleavage of the released material as being a very minor reaction.     

Partition of Volatile Organic Compounds in Activated Sludge and Wastewater

Abstract

The Henry’s law constant is important in the gas-liquid mass transfer process. Apparent dimensionless Henry’s law constant, or the gas-liquid partition coefficient (K’ _H), for both hydrophilic (methanol, isopropyl alcohol, and acetone) and hydrophobic (toluene and p-xylene) organic compounds in deionized (DI) water, a wastewater with a maximum total dissolved organic carbon (DOC) content of 700 mg/L, and DI water mixed with a maximum activated sludge suspended solid (SS) concentration of 40,000 mg/L were measured using the single equilibrium technique at 293 K.

Experimental results demonstrate that the K’ _H of any of the test volatile organic compounds varied among three situations. First, the K’_H of the hydrophilic compounds in mixed liquor with the maximum SS concentration was 9–21% higher than those in DI water. Second, those for toluene and p-xylene were 77% and 93% lower, respectively, in the mixed liquor with the maximum SS concentration. Third, the K’_H values of all of the test compounds in the wastewater were only 10% lower than those in DI water.

A model was developed to relate K’ _H with wastewater DOC and the SS concentration in the activated sludge using an organic carbon-water partition coefficient and activated sludge-water partition coefficient as model parameters. The model was verified and model parameters for test compounds estimated.     

Development of an In-Line System for the Analysis of 4,4′-DDT in Water

An in-line system for trace persistent organic pollutants (POPs) in water was developed by using a laboratory-made hollow fiber membrane (HFM) unit connected with a high-resolution gas chromatograph-mass spectrometer (HRGC-MS). The semivolatile organic compound, 4,4′-Dichlorodiphenyl trichloroethane (4,4′-DDT), was chosen as a representative of a persistent organic compound. The synthetic water contaminated with 4,4′-DDT was passed through the HFM unit, the extraction occurred by the analyte pervaporated and permeated, then stripped into HRGC-MS. Several factors were investigated for the high extraction efficiency. The best performance was obtained at sample and stripping gas flow rates of 6 and 9 mLmin^?1, respectively, and desorption temperature of 60°C. At this temperature, the diffusion rate was enhanced by 15 times over 25°C. A wide linear dynamic range was obtained, i.e., 0.10–1.0 mgL^?1, with a limit of detection (LOD) of 90 μgL^?1. The extraction efficiency of 4,4′-DDT in real water samples was in the range of 83–94%. Real water samples were analyzed and 0.6 μgL^?1 of 4,4′-DDT was found in unregistered bottled water and 7.0 μgL^?1 in tap water.     

Assessing supercritical fluid extraction for the analysis of fipronil,kresoxim-methyl,acrinathrin, and pyridaben residues in melon

An analytical method, using supercritical fluid extraction (SFE), was assessed for residue analysis of the insecticides fipronil, acrinathrin and pyridaben and the fungicide kresoxim-methyl in melons. Extraction conditions were optimized on glass beads, as inert material, evaluating different pressures, temperatures, and CO₂ volumes. Also, the extractability of pesticides from hydromatrix and anhydrous magnesium sulfate was evaluated. Both adsorbents were evaluated for the preparation of SFE-spiked melon samples. Extractions of fortified samples were done using 20 mL of CO₂, 300 atm, and 50°C. Different extraction conditions, including the addition of water and methanol as a static modifier, were used to assess the extractability of these pesticides, and the addition of methanol was demonstrated to improve the extraction of all the studied pesticides.