Photocatalytic degradation of N-heterocyclic aromatics—effects of number and position of nitrogen atoms in the ring

This study demonstrates the influences of position, number of nitrogen (N) atoms and –C–N– or –N=N– linkage present in the six membered heterocyclic compounds such as pyridine, pyrazine, and pyridazine on their photocatalytic degradation by Au, Ag, and Fe⁺² deposited TiO₂ photocatalyst. The photodegradation rate of these heterocyclic compounds follow the order pyridine > pyrazine > pyridazine due to the different extent of hydroxylation and difference in position and number of N atoms in the aromatic moiety. The Au photodeposition significantly improved the TiO₂ photoactivity as compared to Ag and Fe⁺² loading. The presence of two N atoms in pyrazine and pyridazine as compared to one N atom in pyridine hamper the nucleophilc attack of OH radicals in comparison to easy hydroxylation of pyridine ring. There is 1 N atom, 4C–C, 1C–N and 1C=N bond in pyridine, 2 N atoms in the 1 and 4 positions, 2C–C, 2C–N bonds and 2C=N bonds in pyrazine, and pyridazine ring contains 2 N atoms in the 1 and 2 positions, 3C–C, 1N–N bond and 2C=N bonds. The bond strength/energy decreases gradually as: C=N– (615 KJ/mol)?>?–N=N– (418 KJ/mol)?>?–C–C– (347 KJ/mol)?>?–C–N– (305 KJ/mol)?>?–N–N– (163 KJ/mol). As pyridine has 1C–N, 1C=N, and no N–N bond, it photodegrades easily as compared to 1 N–N and 2C=N bonds of pyridazine of lowest photodecomposition rate. The improved photoactivity of Au–TiO₂ is explained on the basis of its favorable redox potential, work function, and electron-capturing capacity, etc.     

acid rain and environmental policy

Editor’s note: This paper by Dr. Jacobson was presented at the 74th annual meeting of the Air Pollution Control Association as part of a panel discussion entitled “Acid Rain–1981: An International Issue.” The session was held on June 22, 1981, and was arranged by APCA’s TT-6 Energy-Environmental Interactions Committee.     

Book reviews

Handbook of Pollution and Hazardous Materials Compliance. N.P. Cheremisinoff and M. Graffia. Marcel Dekker, Inc., New York, 1996, 506 pp. Price $185.00US. ISBN: 0–8247–9704–3.

Good Laboratory Practice Standards: Application for Field and Laboratory Studies. W.Y. Garner, M.S. Barge and J.P. Ussary (Editors). American Chemical Society, Washington, DC 1992. xix + 571 pp. Price $109.95US. ISBN: 0–8412–2192–8.

Pesticides ‐ Developments, Impacts, and Controls. G. Best and D. Ruthven (Editors). The Royal Society of Chemistry , United Kingdom, 1995. x + 180 pp. Price £49.50. ISBN: 0–85404–785–9.

Designing Safer Chemicals: Green Chemistry for Pollution Prevention. S.C. DeVito and R.L. Garrett (Editors). ACS Symposium Series 640, American Chemical Society, Washington, DC 1996. x + 254 pp. Price S89.95US. ISBN:0–8412–3443–4.     

Designing cost efficient buffer zone programs: An application of the FyrisSKZ tool in a Swedish catchment

Riparian buffer zones are the only measure which has been used extensively in Sweden to reduce phosphorus losses from agricultural land. This paper describes how the FyrisSKZ web tool can be used to evaluate allocation scenarios using data from the Svärta River, an agricultural catchment located in central Sweden. Three scenarios are evaluated: a baseline, a uniform 6-m-wide buffer zone in each sub-catchment, and an allocation of areas of buffer zones to sub-catchments based on the average cost of reduction. The total P reduction increases by 30 % in the second scenario compared to the baseline scenario, and the average reduction per hectare increases by 90 % while total costs of the program fall by 32 %. In the third scenario, the average cost per unit of reduction (€163 kg P^?1) is the lowest of the three scenarios (58 % lower than the baseline) and has the lowest total program costs.     

HCI Sorption by Dry NaHCO3 for Incinerator Emissions Control

The sorption of hydrochloric acid (HCI) by thermally decomposed sodium bicarbonate (NaHCO₃) was investigated using a fixed-bed reactor containing sorbent particles dispersed in a bed of spherical glass beads. The gas flow rate (68° F and 760 mm Hg) was 0.039 cfm (1.1 liter/min) and the bed had a cross-sectional area of 0.0055 sq. ft. (5.1 sq. cm). The influence of particle diameter (10, 45 and 163 μm), temperature (225, 275, 375, 455, and 550° F), superficial gas velocity (11 and 21 fpm at reactor conditions, 375° F), and Inlet HCI gas concentration (415 ppm and 760 ppm in N₂, 275 and 455° F) were studied. Results showed that HCI sorption increased strongly with increasing temperature but was only weakly dependent on particle diameter, superficial gas velocity, and HCI gas concentration.     

Characterization of contaminants and evaluation of the suitability for land application of maize and sludge biochars

Prior to the application of biochar as an agricultural improver, attention should be paid to the potential introduction of toxicants and resulting unintended impacts on the environment. In the present study, the concentrations of polycyclic aromatic hydrocarbons (PAHs), heavy metals, and mineral elements were determined in maize and sludge biochars produced at 100 °C increments between 200 and 700 °C. The concentration ranges of total PAHs were 358–5,136 μg kg^?1 in maize biochars and 179–70,385 μg kg^?1 in sludge biochars. The total heavy metals were detected at the following concentrations (mg kg^?1): Cu, 20.4–56.7; Zn, 59.7–133; Pb, 1.44–3.50; Cd, <0.014; Cr, 8.08–21.4; Ni, 4.38–9.82 in maize biochars and Cu, 149–202; Zn, 735–986; Pb, 54.7–74.2; Cd, 1.06–1.38; Cr, 180–247; Ni, 41.1–56.1 in sludge biochars. The total concentrations of PAHs and heavy metals in all maize biochars and most sludge biochars were below the control standards of sludge for agricultural use in China, the USA, and Europe. The leachable Mn concentrations in sludge biochars produced at below 500 °C exceeded the groundwater or drinking water standards of these countries. Overall, all the maize biochars were acceptable for land application, but sludge biochars generated at temperatures between 200 and 500 °C were unsuitable for application as soil amendments due to their potential adverse effects on soil and groundwater quality.     

Chemically coupled microwave and ultrasonic pre-hydrolysis of pulp and paper mill waste-activated sludge: effect on sludge solubilisation and anaerobic digestion

The effects of alkali-enhanced microwave (MW; 50–175 °C) and ultrasonic (US) (0.75 W/mL, 15–60 min) pretreatments, on solubilisation and subsequent anaerobic digestion efficiency of pulp and paper mill waste-activated sludge, were investigated. Improvements in total chemical oxygen demand and volatile suspended solids (VSS) solubilisation were limited to 33 and 39 % in MW pretreatment only (175 °C). It reached 78 and 66 % in combined MW–alkali pretreatment (pH 12?+?175 °C), respectively. Similarly, chemical oxygen demand and VSS solubilisation were 58 and 37 % in US pretreatment alone (60 min) and it improved by 66 and 49 % after US–alkali pretreatment (pH 12?+?60 min), respectively. The biogas yield for US 60 min–alkali (pH 12)-pretreated sludge was significantly improved by 47 and 20 % over the control and US 60 reactors, respectively. The biogas generation for MW (150 °C)–alkali (pH 12)-pretreated sludge was only 6.3 % higher than control; however, it was 8.3 % lower than the MW (150 °C) reactor, which was due to the inhibition of anaerobic activity under harsh thermal–alkali treatment condition.     

Suitability of passive sampling for the monitoring of pharmaceuticals in Finnish surface waters

The occurrence of five pharmaceuticals, consisting of four anti-inflammatory and one antiepileptic drug, was studied by passive sampling and grab sampling in northern Lake Päijänne and River Vantaa. The passive sampling was performed by using Chemcatcher® sampler with a SDB-RPS Empore disk as a receiving phase. In Lake Päijänne, the sampling was conducted during summer 2013 at four locations near the discharge point of a wastewater treatment plant and in the years 2013 and 2015 at four locations along River Vantaa. The samples were analyzed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) in the multiple reaction monitoring mode. The concentrations of carbamazepine, diclofenac, ibuprofen, ketoprofen, and naproxen in Lake Päijänne determined by passive sampling ranged between 1.4–2.9 ng L^?1, 15–35 ng L^?1, 13–31 ng L^?1, 16–27 ng L^?1, and 3.3–32 ng L^?1, respectively. Similarly, the results in River Vantaa ranged between 1.2–40 ng L^?1, 15–65 ng L^?1, 13–33 ng L^?1, 16–31 ng L^?1, and 3.3–6.4 ng L^?1. The results suggest that the Chemcatcher passive samplers are suitable for detecting pharmaceuticals in lake and river waters.     

Mineral constituents in Leccinum scabrum from lowland locations in the central Europe and their relation to concentration in forest topsoil

Leccinum scabrum is an edible mushroom common in European regions in the northern hemisphere. Macro and trace mineral constituents such as Ag, Al, Ba, Ca, Cd, Co, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, P, Rb, Sr and Zn were studied in L. scabrum and in the top soil collected from the same location underneath soil substratum. The “pseudo-total” and labile (extractable fraction of minerals) were measured to get insight into the levels, distribution between the morphological parts of fruiting bodies, potential for their bioconcentration by mushroom and evaluated for human exposure via consumption of the mushroom. The sampling sites include the Dar?lubska Wilderness, Trójmiejski Landscape Park, Sobieszewo Island, Wdzydze Landscape Park and outskirts of the K?trzyn town in Mazury from the norther part of Poland. Median values of K, Rb and P concentrations in dehydrated L. scabrum were for caps in range 27,000–44,000 mg kg^?1, 90–320 mg kg^?1 and 6,200–9,100 mg kg^?1, and followed by Mg at 880–1,000 mg kg^?1, Ca at 48–210 mg kg^?1 and Al at 15–120 mg kg^?1. The median concentrations of Cu, Fe, Mn and Zn in caps were in range 15–27 mg kg^?1 db 38–140 mg kg^?1, 5.3–27 mg kg^?1 and 130–270 mg kg^?1. For Ba and Sr, concentrations on the average were at ～1 mg kg^?1, and almost equally distributed between the caps and stipes of the fruiting bodies. L. scabrum mushrooms were low in toxic Ag, Cd, Hg and Pb, for which the median values in dried caps from five locations were, respectively, in range 0.48–0.98 mg kg^?1 (cap to stipe index, Q_C/S, was 2.5–4.1), 1.0–5.8 mg kg^?1 (Q_C/S 2.9–3.8), 0.36–0.59 mg kg^?1 (Q_C/S 1.6–2.7) and 0.20–0.91 mg kg^?1 (Q_C/S 1.2–1.9). Substantial variations in the concentrations of the “pseudo-total” fraction (extracted by aqua regia) or labile fraction (extracted by 20% solution of nitric acid) of the elements determined in forest topsoils were noted between some of the locations examined. The elements K, P, Cd, Cu, Hg, Mn, Na, Rb and Zn can be considered as those which were bioconcentrated by L. scabrum in fruiting bodies, while the rates of accumulation varied with the sampling location.     

Simultaneous determination of eight metabolites of organophosphate and pyrethroid pesticides in urine

A simultaneous method for quantifying eight metabolites of organophosphate pesticides and pyrethroid pesticides in urine samples has been established. The analytes were extracted using liquid–liquid extraction coupled with WCX solid phase extraction (SPE) cartridges. Eight metabolites were chemically derivatized before analysis using gas chromatography–tandem mass spectrometry (GC–MS–MS). The separation was performed on a HP-5MS capillary column (30 m × 0.25 mm × 0.25 µm) with temperature programming. The detection was performed under electro-spray ionization (ESI) in multiple reaction monitoring (MRM) mode. An internal standard method was used. The extraction solvent, types of SPE cartridges and eluents were optimized by comparing the sample recoveries under different conditions. The results showed that the calibration curves of the five organophosphorus pesticides metabolites were linear in the range of 0.2–200 μg/L (r² ≥ 0.992) and that of the three pyrethroid pesticides metabolites were linear in the range of 0.025–250 μg/L (r² ≥ 0.991). The limits of detection (LODs, S/N ≥ 3) and the limits of quantification (LOQs, S/N ≥ 10) of the eight metabolites were 0.008–0.833 μg/L and 0.25–2.5 μg/L, respectively. The recoveries of the eight metabolites ranged from 54.08% to 82.49%. This efficient, stable, and cost-effective method is adequate to handle the large number of samples required for surveying the exposure level of organophosphorus and pyrethroid pesticides in the general population.     

Neutral poly- and perfluoroalkyl substances in air and seawater of the North Sea

Concentrations of neutral poly- and perfluoroalkyl substances (PFASs), such as fluorotelomer alcohols (FTOHs), perfluoroalkane sulfonamides (FASAs), perfluoroalkane sufonamidoethanols (FASEs), and fluorotelomer acrylates (FTACs), have been simultaneously determined in surface seawater and the atmosphere of the North Sea. Seawater and air samples were taken aboard the German research vessel Heincke on the cruise 303 from 15 to 24 May 2009. The concentrations of FTOHs, FASAs, FASEs, and FTACs in the dissolved phase were 2.6–74, <0.1–19, <0.1–63, and <1.0–9.0 pg L^?1, respectively. The highest concentrations were determined in the estuary of the Weser and Elbe rivers and a decreasing concentration profile appeared with increasing distance from the coast toward the central part of the North Sea. Gaseous FTOHs, FASAs, FASEs, and FTACs were in the range of 36–126, 3.1–26, 3.7–19, and 0.8–5.6 pg m^?3, which were consistent with the concentrations determined in 2007 in the North Sea, and approximately five times lower than those reported for an urban area of Northern Germany. These results suggested continuous continental emissions of neutral PFASs followed by transport toward the marine environment. Air–seawater gas exchanges of neutral PFASs were estimated using fugacity ratios and the two-film resistance model based upon paired air–seawater concentrations and estimated Henry's law constant values. Volatilization dominated for all neutral PFASs in the North Sea. The air–seawater gas exchange fluxes were in the range of 2.5?×?10³–3.6?×?10⁵ pg m^?2 for FTOHs, 1.8?×?10²–1.0?×?10⁵ pg m^?2 for FASAs, 1.1?×?10²–3.0?×?10⁵ pg m^?2 for FASEs and 6.3?×?10²–2.0?×?10⁴ pg m^?2 for FTACs, respectively. These results suggest that the air–seawater gas exchange is an important process that intervenes in the transport and fate for neutral PFASs in the marine environment.     

Determination of phenols and pharmaceuticals in municipal wastewaters from Polish treatment plants by ultrasound-assisted emulsification–microextraction followed by GC–MS

A method combining ultrasound-assisted emulsification–microextraction (USAEME) with gas chromatography–mass spectrometry (GC–MS) was developed for simultaneous determination of four acidic pharmaceuticals, ibuprofen, naproxen, ketoprofen, and diclofenac, as well as four phenols, 4-octylphenol, 4-n-nonylphenol, bisphenol A, and triclosan in municipal wastewaters. Conditions of extraction and simultaneous derivatization were optimized with respect to such aspects as type and volume of extraction solvent, volume of derivatization reagent, kind and amount of buffering salt, location of the test tube in the ultrasonic bath, and extraction time. The average correlation coefficient of the calibration curves was 0.9946. The LOD/(LOQ) values in influent and effluent wastewater were in the range of 0.002–0.121/(0.005–0.403) μg L^?1 and 0.002–0.828/(0.006–2.758) μg L^?1, respectively. Quantitative recoveries (≥94 %) and satisfactory precision (average RSD 8.2 %) were obtained. The optimized USAEME/GC–MS method was applied for determination of the considered pharmaceuticals and phenols in influents and treated effluents from nine Polish municipal wastewater treatment plants. The average concentration of acidic pharmaceuticals in influent and effluent wastewater were in the range of 0.06–551.96 μg L^?1 and 0.01–22.61 μg L^?1, respectively, while for phenols were in the range of 0.03–102.54 μg L^?1 and 0.02–10.84 μg L^?1, respectively. The removal efficiencies of the target compounds during purification process were between 84 and 99 %.     

Distribution and Fractionation of Phosphorus,Cadmium, Nickel,and Lead in Calcareous Soils Amended with Composts

Abstract

Composts improve organic carbon content and nutrients of calcareous soils but the accumulation and distribution of phosphorus and heavy metals among various fractions in soil may vary under the south Florida conditions. The accumulation of P, Cd, Ni, and Pb with depth and the distribution of water soluble, exchangeable, carbonate, Fe–Mn oxides, organic and residual forms of each element were investigated in soils amended with municipal solid waste (MSW) compost, co-compost and biosolids compost and inorganic fertilizer (as control). Total concentrations of P, Cd, Ni, and Pb were higher in the 0–22 cm soil layers and decreased considerably in the rock layers. These elements were in the decreasing order of P ? Pb > Ni > Cd. Amounts of water soluble and exchangeable forms of P, Cd, Ni and Pb were negligible at 0–22 cm soil depths except for Cd in the 10–22 cm depth. Amending calcareous soil with either organic or inorganic amendments rendered phosphorus, nickle and lead in the residual form followed by Fe–Mn oxides form in the 0–10 and 10–22 cm soil layers. Cadmium was predominantly in the Fe–Mn oxides fraction followed by the residual and carbonate forms in both soil layers. A significant positive correlation was found between various organic carbon fractions and organic forms of P, Cd and Pb in the surface soil layer. Soil amended with MSW compost had higher concentration of Cd in the organic fraction whereas, co-compost and MSW compost amended soil had higher concentrations of organic Ni fraction in the 0–10 cm soil layer.     

Composition and effects of inhalable size fractions of atmospheric aerosols in the polluted atmosphere: Part I. PAHs,PCBs and OCPs and the matrix chemical composition

Atmospheric particulate matter (PM) abundance, mass size distribution (MSD) and chemical composition are parameters relevant for human health effects. The MSD and phase state of semivolatile organic pollutants were determined at various polluted sites in addition to the PM composition and MSD. The distribution pattern of pollutants varied from side to side in correspondence to main particle sources and PM composition. Levels of particle-associated polycyclic aromatic hydrocarbons (PAHs) were 1–30 ng m^?3 (corresponding to 15–35 % of the total, i.e., gas and particulate phase concentrations), of polychlorinated biphenyls (PCBs) were 2–11 pg m^?3 (4–26 % of the total) and of DDT compounds were 2–12 pg m^?3 (4–23 % of the total). The PM associated amounts of other organochlorine pesticides were too low for quantification. The organics were preferentially found associated with particles <0.45 μm of aerodynamic equivalent diameter. The mass fractions associated with sub-micrometer particles (PM_0.95) were 73–90 %, 34–71 % and 36–81 % for PAHs, PCBs and DDT compounds, respectively. The finest particles fraction had the highest aerosol surface concentration (6.3–29.7)_×10^?6 cm^?1 (44–70 % of the surface concentration of all size fractions). The data set was used to test gas-particle partitioning models for semivolatile organics for the first time in terms of the organics' MSD and size-dependent PM composition. The results of this study prove that at the various sites particles with diverse size, matrix composition, amount of contaminants and toxicological effects occur. Legislative regulation based on gravimetric determination of PM mass can clearly be insufficient for assessment.     

The acute effects of fine particles on respiratory mortality and morbidity in Beijing, 2004–2009

Recent epidemiological and toxicological studies have shown associations between particulate matter and human health. However, the estimates of adverse health effects are inconsistent across many countries and areas. The stratification and interaction models were employed within the context of the generalized additive Poisson regression equation to examine the acute effects of fine particles on respiratory health and to explore the possible joint modification of temperature, humidity, and season in Beijing, China, for the period 2004–2009. The results revealed that the respiratory health damage threshold of the PM_2.5 concentration was mainly within the range of 20–60 μg/m³, and the adverse effect of excessively high PM_2.5 concentration maintained a stable level. In the most serious case, an increase of 10 μg/m³ PM_2.5 results in an elevation of 4.60 % (95 % CI 3.84–4.60 %) and 4.48 % (95 % CI 3.53–5.41 %) with a lag of 3 days, values far higher than the average level of 0.69 % (95 % CI 0.54–0.85 %) and 1.32 % (95 % CI 1.02–1.61 %) for respiratory mortality and morbidity, respectively. There were strong seasonal patterns of adverse effects with the seasonal variation of temperature and humidity. The growth rates of respiratory mortality and morbidity were highest in winter. And, they increased 1.4 and 1.8 times in winter, greater than in the full year as PM_2.5 increased 10 μg/m³.     

Occurrence of free estrogens,conjugated estrogens,and bisphenol A in fresh livestock excreta and their removal by composting in North China

An efficient pretreatment and analytical method was developed to investigate the occurrence and fate of four free estrogens (estrone (E1), 17β-estradiol (17β-E2), estriol (E3), and 17α-ethinylestradiol (EE2)), four conjugated estrogens (estrone-3-sulfate sodium salt (E1-3S), 17β-estradiol-3-sulfate sodium salt (E2-3S), estrone-3-glucuronide sodium salt (E1-3G), and 17β-estradiol-3-glucuronide sodium salt (E2-3G)), and bisphenol A (BPA) in three livestock farms raising beef cattle, cows, sheep, swine, and chickens in Qi County, which is located in North China. The results demonstrated that one cow and one beef cattle excreted 956.25–1,270.41 and 244.38–319.99 μg/day of total (free and conjugated) estrogen, respectively, primarily through feces (greater than 91 %), while swine excreted 260.09–289.99 μg/day of estrogens, primarily through urine (98–99 %). The total estrogen excreted in sheep and broiler chicken feces was calculated to be 21.64–28.67 and 4.62–5.40 μg/day, respectively. It was determined that conjugated estrogens contributed to 21.1–21.9 % of the total estrogen excreted in cow feces and more than 98 % of the total estrogen excreted in swine urine. After composting, the concentration of total estrogen decreased by 18.7–59.6 %; however, increased levels of BPA were measured. In treated compost samples, estrogens were detected at concentrations up to 74.0 ng/g, which indicates a potential risk of estrogens entering the surrounding environment.     

Sorption–desorption and transport of trimethoprim and sulfonamide antibiotics in agricultural soil: effect of soil type,dissolved organic matter,and pH

Use of animal manure is a main source of veterinary pharmaceuticals (VPs) in soil and groundwater through a series of migration processes. The sorption–desorption and transport of four commonly used VPs including trimethoprim (TMP), sulfapyridine, sulfameter, and sulfadimethoxine were investigated in three soil layers taken from an agricultural field in Chongming Island China and two types of aqueous solution (0.01 M CaCl₂ solution and wastewater treatment plant effluent). Results from sorption–desorption experiments showed that the sorption behavior of selected VPs conformed to the Freundlich isotherm equation. TMP exhibited higher distribution coefficients (K _d?=?6.73–9.21) than other sulfonamides (K _d?=?0.03–0.47), indicating a much stronger adsorption capacity of TMP. The percentage of desorption for TMP in a range of 8–12 % is not so high to be considered significant. Low pH (<pK _a of tested VPs) and rich soil organic matter (e.g., 0–20 cm soil sample) had a positive impact on sorption of VPs. Slightly lower distribution coefficients were obtained for VPs in wastewater treatment plant (WWTP) effluent, which suggested that dissolved organic matter might affect their sorption behavior. Column studies indicated that the transport of VPs in the soil column was mainly influenced by sorption capacity. The weakly adsorbed sulfonamides had a high recovery rate (63.6–98.0 %) in the leachate, while the recovery rate of TMP was only 4.2–10.4 %. The sulfonamides and TMP exhibited stronger retaining capacity in 20–80 cm and 0–20 cm soil samples, respectively. The transport of VPs was slightly higher in the columns leached by WWTP effluent than by CaCl₂ solution (0.01 M) due to their sorption interactions.     

Dissipation pattern of flubendiamide residues on capsicum fruit (Capsicum annuum L.) under field and controlled environmental conditions

This investigation was undertaken to compare the dissipation pattern of flubendiamide in capsicum fruits under poly-house and open field after giving spray applications at the recommended and double doses of 48 g a.i. ha^?1 and 96 g a.i. ha^?1. Extraction and purification of capsicum fruit samples were carried out by the QuEChERS method. Residues of flubendiamide and its metabolite, des-iodo flubendiamide, were analyzed by high-performance liquid chromatography–photodiode array, and confirmed by liquid chromatography–mass spectrometry/mass spectrometry. Limit of quantification of the method was 0.05 mg kg^?1, and recovery of the insecticides was in the range of 89.6–104.3%, with relative standard deviation being 4.5–11.5%. The measurement uncertainty of the analytical method was in the range of 10.7–15.7%. Initial residue deposits of flubendiamide on capsicum fruits grown under poly-house conditions were (0.977 and 1.834 mg kg^?1) higher than that grown in the field (0.665 and 1.545 mg kg^?1). Flubendiamide residues persisted for 15 days in field-grown and for 25 days in poly-house-grown capsicum fruits. The residues were degraded with the half-lives of 4.3–4.7 and 5.6–6.6 days in field and poly-house respectively. Des-iodo flubendiamide was not detected in capsicum fruits or soil. The residues of flubendiamide degraded to below the maximum residue limit notified by Codex Alimentarius Commission (FAO/WHO) after 1 and 6 days in open field, and 3 and 10 days in poly-house. The results of the study indicated that flubendiamide applied to capsicum under controlled environmental conditions required longer pre-harvest interval to allow its residues to dissipate to the safe level.     

Tropical surface water quality studies: Implications for the aquatic fate of N-methyl carbamate pesticides

Water quality assessment was conducted on the Ruiru River, a tributary of an important tropical river system in Kenya, to determine baseline river conditions for studies on the aquatic fate of N-methyl carbamate (NMC) pesticides. Measurements were taken at the end of the long rainy season in early June 2013. Concentrations of copper (0.21–1.51 ppm), nitrates (2.28–4.89 ppm) and phosphates (0.01–0.50 ppm) were detected at higher values than in uncontaminated waters, and attributed to surface runoff from agricultural activity in the surrounding area. Concentrations of dissolved oxygen (8–10 ppm), ammonia (0.02–0.22 ppm) and phenols (0.19–0.83 ppm) were found to lie within normal ranges. The Ruiru River was found to be slightly basic (pH 7.08–7.70) with a temperature of 17.8–21.2°C. The half-life values for hydrolysis of three NMC pesticides (carbofuran, carbaryl and propoxur) used in the area were measured under laboratory conditions, revealing that rates of decay were influenced by the electronic nature of the NMCs. The hydrolysis half-lives at pH 9 and 18°C decreased in the order carbofuran (57.8 h) > propoxur (38.5 h) > carbaryl (19.3 h). In general, a decrease in the electron density of the NMC aromatic ring increases the acidity of the N-bound proton removed in the rate-limiting step of the hydrolysis mechanism. Our results are consistent with this prediction, and the most electron-poor NMC (carbaryl) hydrolyzed fastest, while the most electron-rich NMC (carbofuran) hydrolyzed slowest. Results from this study should provide baseline data for future studies on NMC pesticide chemical fate in the Ruiru River and similar tropical water systems.     

Method Development for Determination of Fluroxypyr in Soil

Abstract

Four methods were developed for the analysis of fluroxypyr in soil samples from oil palm plantations. The first method involved the extraction of the herbicide with 0.05 M NaOH in methanol followed by purification using acid base partition. The concentrated material was subjected to derivatization and then cleaning process using a florisil column and finally analyzed by gas chromatography (GC) equipped with electron capture detector (ECD). By this method, the recovery of fluroxypyr from the spiked soil ranged from 70 to 104% with the minimum detection limit at 5 µg/kg. The second method involved solid liquid extraction of fluroxypyr using a horizontal shaker followed by quantification using high performance liquid chromatography (HPLC) equipped with UV detector. The recovery of fluroxypyr using this method, ranged from 80 to 120% when the soil was spiked with fluroxypyr at 0.1–0.2 µg/g soil. In the third method, the recovery of fluroxypyr was determined by solid liquid extraction using an ultrasonic bath. The recovery of fluroxypyr at spiking levels of 4–50 µg/L ranged from 88 to 98% with relative standard deviations of 3.0–5.8% with a minimum detection limit of 4 µg/kg. In the fourth method, fluroxypyr was extracted using the solid liquid extraction method followed by the cleaning up step with OASIS® HLB (polyvinyl dibenzene). The recovery of fluroxypyr was between 91 and 95% with relative standard deviations of 4.2–6.2%, respectively. The limit of detection in method 4 was further improved to 1 µg/kg. When the weight of soil used was increased 4 fold, the recovery of fluroxypyr at spiking level of 1–50 µg/kg ranged from 82–107% with relative standard deviations of 0.5–4.7%.