Volatile organic compounds in air at urban and industrial areas in the Tarragona region by thermal desorption and gas chromatography–mass spectrometry

Annual trends of a group of 66 volatile organic compounds (VOCs), containing 20 ozone precursors, were the aim of a sampling campaign carried out for a year in air at urban and industrial areas from Tarragona region. VOCs were determined by active collection on multisorbent tubes, followed by thermal desorption and gas chromatography–mass spectrometry. The analytical method was developed and validated, showing good levels of detection and quantification, recoveries, precision, and linearity for all the compounds in the range being studied. All the industrial and urban samples taken during the sampling campaign were similar in their qualitative composition. The most abundant compound in all urban and industrial sites was i-pentane, with concentrations between 15.2 and 202.1 μg m^???3 in urban sites and between 1.3 and 98.6 μg m^???3 in industrial sites. In urban sites, the following compounds in order of abundance were toluene, n-pentane, m,p-xylene, and o-xylene, with maximum levels of 150.6, 45.8, 42.3, and 31.7 μg m^???3, respectively. In industrial sites, the most abundant compounds depended on the sampled site.     

Single drop microextraction and gas chromatography–mass spectrometry for the determination of diflufenican, mepanipyrim, fipronil, and pretilachlor in water samples

An analytical method for the determination of diflufenican, mepanipyrim, pretilachlor, and fipronil in water samples was developed using single drop microextraction in the direct immersion mode and gas chromatography–mass spectrometry. A factorial fractionated design of type 2^6–1 at two levels was performed, to study the influence of experimental variables such as ionic strength, pH, agitation speed, extraction time, drop volume, and sample volume. To establish the optimal conditions for the variables that were significant, a Doehlert design was performed. The optimum conditions of extraction were 1 μL of heptane immersed in 4.0 mL of sample with continuous agitation at 500 rpm for 30 min at room temperature. The developed method proved to have good linearity for the range studied. The detection limits were 0.07 μg L^?1 for diflufenican, 0.03 μg L^?1 for mepanipyrim, 0.08 μg L^?1 for pretilachlor, and 1.39 μg L^?1 for fipronil. The method was validated on river water samples, showing the absence of matrix effect and recoveries ranged from 90.1 to 107.8 %. The results show that the method developed is accurate, sensitive, rapid, simple, and low cost, so it is recommended for application in the analysis of these different classes of pesticides in water samples.     

Simultaneous derivatization and extraction of nitrophenols in soil and rain samples using modified hollow-fiber liquid-phase microextraction followed by gas chromatography–mass spectrometry

A simple and sensitive method based on a modified hollow-fiber liquid-phase microextraction followed by gas chromatography–mass spectrometry has been successfully developed for the extraction and simultaneous derivatization of some nitrophenols (NPs) in soil and rain samples. Microwave-assisted solvent extraction was used for the extraction of NPs from the soil, while the rain sample was directly applied to the previously mentioned method. Briefly, in this method, the analytes were extracted from aqueous samples into a thin layer of organic solvent (dodecane?+?10 % tri-n-octylphosphine oxide) sustained in the pores of a porous hollow fiber. Then, they were back-extracted using a small volume of organic acceptor solution (25 μl; 10 mg/L N-methyl-N-(trimethylsilyl)trifluoroacetamide, as derivatization reagent, in acetonitrile) that was located inside the lumen of the hollow fiber. Under the optimized extraction conditions, enrichment factors of 255 to 280 and limits of detection of 0.1 to 0.2 μg/L (S/N?=?3) with dynamic linear ranges of 1–100 μg/L were obtained for the analytes. The accuracy of the approach was tested by the relative recovery experiments on spiked samples, with results ranging from 93 to 113 %. The method was shown to be rapid, cost-effective, and potentially interesting for screening purposes.     

Residue analysis of acephate and its metabolite methamidophos in open field and greenhouse pakchoi (Brassica campestris L.) by gas chromatography–tandem mass spectrometry

To analysze the dynamic degradation and final residues of acephate and its metabolite methamidophos, field-experiments with pakchoi (Brassica campestris L.) in open field and greenhouse were carried out in Beijing, China in 2004 and 2005. The degradation dynamics and final residues were determined by gas chromatography (GC) equipped with a pulsed flame photometric detector and GC coupled to mass spectrometry (MS)/MS after acephate was applied on open field and green house pakchoi (B. campestris L.). The dynamic degradation results showed that the half-lives of acephate and methamidophos in open field pakchoi were 1.36 days with dynamic degradation equation C _t ?=?133.01e^???0.5107t , and 2.86 days with C _t ?=?6.5753e^???0.2422t , respectively. While the half-lives of acephate and methamidophos in the greenhouse were 1.07 days with C _t ?=?59.134e^???0.4353t and 0.79 days with C _t ?=?0.2703e^???0.2595t , respectively. The final residue analysis demonstrated that >50% of total methamidophos were resulted from the degradation of acephate 7 and 18 days after it was applied on the greenhouse pakchoi, respectively. While in the open-field pakchoi, >90% of total methamidophos was found to be the metabolite of acephate.     

Effect of process conditions on the analysis of free and conjugated estrogen hormones by solid-phase extraction–gas chromatography/mass spectrometry (SPE–GC/MS)

Simultaneous analysis of 11 free estrogen hormones and five conjugated estrogens in water and municipal wastewater was studied. The analytical method was developed and tested for different types of solid-phase extraction adsorbents, eluents, sample containers and storage conditions, derivatization, and matrix effects. Varian Bond Elut C-18 solid-phase extraction adsorbent cartridge was selected based on its high recoveries for both free and conjugated estrogens. Sample storage conditions, as well as selection and pretreatment of sample container materials, can affect the trace level analysis of estrogens. Silanization of glassware is observed to provide low relative standard deviation (RSD) in the analysis and less percentage loss due to contacting with sample container materials. Light exposure during the test can significantly impact the results. The derivatized samples stored at −20°C for at least 6 days showed less than 10.5% average RSD in the analysis. The recovery efficiency in clean water varies from 72% to 101% for free estrogens and 78% to 82% for conjugated estrogens. The method detection limits (MDL) for most of the compounds range from 30 to 870 ng/L using a sample volume of 200 mL. With a sample volume of 3 L, the most sensitive compound produces a MDL of 0.03 ng/L. Dilute methanol is used to wash the loaded cartridge as a cleanup step in order to remove interfering species during analysis of wastewater samples. Using the optimized analytical methods, the concentration level of free estrogens in the influent and effluent municipal wastewaters is tested.     

Estimation of chlorpyriphos and cypermethrin residues in chilli (Capsicum annuum L.) by gas–liquid chromatography

Dissipation of chlorpyriphos and cypermethrin in chilli was studied following three applications of a combination formulation of Nurelle-D 505 (chlorpyriphos 50 %?+?cypermethrin 5 %) at 1 and 2 L?ha^?1 at an interval of 15 days. Residues of chlorpyriphos and cypermethrin in chilli were estimated by gas–liquid chromatography and confirmed by gas chromatography–mass spectrometry. Half-life periods for chlorpyriphos were found to be 4.43 and 2.01 days, whereas for cypermethrin these values were observed to be 2.51 and 2.64 days at single and double the application rates, respectively. Residues of chlorpyriphos dissipated to more than 80 % after 10 days at both the dosages. However, residues of cypermethrin dissipated to the extent of more than 70 % in 7 days. Soil samples collected after 15 days of the last application did not show the presence of chlorpyriphos and cypermethrin at their respective determination limit of 0.01 mg?kg^?1. The use of chlorpyriphos and cypermethrin mixture at the recommended dosage does not seem to pose any hazards to the consumers, and a waiting period of 1 day is suggested to reduce the risk before consumption of green chilli.     

The occurrence of glyphosate, atrazine, and other pesticides in vernal pools and adjacent streams in Washington, DC, Maryland, Iowa, and Wyoming, 2005–2006

Vernal pools are sensitive environments that provide critical habitat for many species, including amphibians. These small water bodies are not always protected by pesticide label requirements for no-spray buffer zones, and the occurrence of pesticides in them is poorly documented. In this study, we investigated the occurrence of glyphosate, its primary degradation product aminomethylphosphonic acid, and additional pesticides in vernal pools and adjacent flowing waters. Most sampling sites were chosen to be in areas where glyphosate was being used either in production agriculture or for nonindigenous plant control. The four site locations were in otherwise protected areas (e.g., in a National Park). When possible, water samples were collected both before and after glyphosate application in 2005 and 2006. Twenty-eight pesticides or pesticide degradation products were detected in the study, and as many as 11 were identified in individual samples. Atrazine was detected most frequently and concentrations exceeded the freshwater aquatic life standard of 1.8 micrograms per liter (microg/l) in samples from Rands Ditch and Browns Ditch in DeSoto National Wildlife Refuge. Glyphosate was measured at the highest concentration (328 microg/l) in a sample from Riley Spring Pond in Rock Creek National Park. This concentration exceeded the freshwater aquatic life standard for glyphosate of 65 microg/l. Aminomethylphosphonic acid, triclopyr, and nicosulfuron also were detected at concentrations greater than 3.0 microg/l.     

Greenhouse gas mitigation in rice–wheat system with leaf color chart-based urea application

Conventional blanket application of nitrogen (N) fertilizer results in more loss of N from soil system and emission of nitrous oxide, a greenhouse gas (GHG). The leaf color chart (LCC) can be used for real-time N management and synchronizing N application with crop demand to reduce GHG emission. A 1-year study was carried out to evaluate the impact of conventional and LCC-based urea application on emission of nitrous oxide, methane, and carbon dioxide in a rice–wheat system of the Indo-Gangetic Plains of India. Treatments consisted of LCC scores of ≤4 and 5 for rice and wheat and were compared with conventional fixed-time N splitting schedule. The LCC-based urea application reduced nitrous oxide emission in rice and wheat. Application of 120 kg N per hectare at LCC ≤ 4 decreased nitrous oxide emission by 16% and methane by 11% over the conventional split application of urea in rice. However, application of N at LCC ≤ 5 increased nitrous oxide emission by 11% over the LCC ≤ 4 treatment in rice. Wheat reduction of nitrous oxide at LCC ≤ 4 was 18% as compared to the conventional method. Application of LCC-based N did not affect carbon dioxide emission from soil in rice and wheat. The global warming potential (GWP) were 12,395 and 13,692 kg CO₂ ha⁻¹ in LCC ≤ 4 and conventional urea application, respectively. Total carbon fixed in conventional urea application in rice–wheat system was 4.89 Mg C ha⁻¹ and it increased to 5.54 Mg C ha⁻¹ in LCC-based urea application (LCC ≤ 4). The study showed that LCC-based urea application can reduce GWP of a rice–wheat system by 10.5%.     

Forecasts using Box–Jenkins models for the ambient air quality data of Delhi City

The monthly maximum of the 24-h average time-series data of ambient air quality-sulphur dioxide (SO(2)), nitrogen dioxide (NO(2)) and suspended particulate matter (SPM) concentration monitored at the six National Ambient Air Quality Monitoring (NAAQM) stations in Delhi, was analysed using Box-Jenkins modelling approach (Box et al. 1994). Univariate linear stochastic models were developed to examine the degree of prediction possible for situations where only the past record of pollutant data are available. In all, 18 models were developed, three for each station for each of the respective pollutant. The model evaluation statistics suggest that considerably satisfactory real-time forecasts of pollution concentrations can be generated using the Box-Jenkins approach. The developed models can be used to provide short-term, real-time forecasts of extreme air pollution concentrations for the Air Quality Control Region (AQCR) of Delhi City, India.     

Application of zirconium–iridium permanent modifier for the simultaneous determination of lead, cadmium, arsenic, and nickel in atmospheric particulate matter by multi-element electrothermal atomic absorption spectrometry

A novel and robust method for the simultaneous determination of lead, cadmium, arsenic, and nickel in atmospheric particulate matter by multi-element electrothermal atomic absorption spectrometry was developed, using zirconium–iridium coating as permanent modifier (140 μg Zr and 4 μg Ir). After 300 atomization cycles, it was necessary to add 2 μg of Ir. Due to the varying concentrations of Pb in atmospheric particulate matter, lead was monitored at two wavelengths, at the less sensitive line of 261.4 nm for high concentration samples (>20 μg?L^?1) or at 283.3 nm for the low concentration samples. Matrix-matched calibration had to be performed for quantitative recoveries (96–102 %). Following this approach, the four elements were determined in atmospheric particulate matter samples from an industrial area near the city of Athens in two different time periods (cold–warm) with limits of detection of 5.5 ng?m^?3 for Pb at 261.4 nm and 0.29 ng?m^?3 at 283.3 nm, 0.019 ng?m^?3 for Cd, 0.14 ng?m^?3 for As, and 0.22 ng?m^?3 for Ni. Lead, Cd, and As levels were very low, whereas Ni content was at comparable levels with other areas worldwide.     

Cloud point extraction–atomic absorption spectrometry for pre-concentration and determination of cadmium in cigarette samples

A new complexing agent, 2-((2-((1H-benzo[d]imidazole-2yl)methoxy)phenoxy)methyl)-1H-benzo[d]imidazole (BIMPI), was used in cloud point extraction and applied for selective pre-concentration of trace amounts of cadmium in cigarette samples. Cadmium was complexed with BIMPI in a buffer solution (pH?=?10) using Triton X-114 as surfactant and quantitatively extracted into a small volume of the surfactant-rich phase after centrifugation. Under optimized conditions (pH?=?10.0, 0.8?×?10^?4?mol?L^?1 BIMPI and 0.08 % (w/v) Triton X-114), calibration graph was linear in the range of 34.0–1,670.0 μg?L^?1. The proposed method was applied to the determination of Cd in various cigarette (tobacco) samples which gave satisfactory results.     

Is PM10 mass measurement a reliable index for air quality assessment? An environmental study in a geographical area of north-eastern Italy

The aim of this study was to measure the concentration of some metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Ti) in PM(10) samples collected in one urban and one industrial site and to assess that PM(10) total mass measurement may be not sufficient as air quality index due to its complex composition. Metals were determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and differential pulsed anodic stripping voltammetry (DPASV). The measured concentrations were used to calculate the content of metals in the PM(10) total mass, and to estimate the enrichment factors and the correlations between PM(10), metal concentrations and meteorological data for the two sites. The mean PM10 concentration during the sampling period in the urban site exceeded the annual European Union (EU) standard (40 microg/m(3)) and, for some sampling days, the daily EU standard (50 microg/m(3)) was also exceeded. In opposite, both EU standards were never exceeded in the industrial site. The overall metal content was nearly double in the industrial site compared to the urban one, and the mean Ni concentration exceeded the EU annual limit value (10 ng/m(3)). The metals with the highest enrichment factor were Cd, Cu, Ni and Pb for both sites, suggesting a dominant anthropogenic source for these metals. Metal concentrations were very low and typical of rural background during Christmas holidays, when factories were closed. PM(10) total mass measurement is not a sufficient air quality index since the metal content of PM(10) is not related to its total mass, especially in sites with industrial activities. This measurement should be associated with the analysis of toxic metals.     

PAHs in soils and estimated air�Csoil exchange in the Pearl River Delta, South China

In this study, 74 soil samples collected from the Pearl River Delta were analyzed for polycyclic aromatic hydrocarbons (PAHs). The PAH mixture in the soils is mainly of low molecular weight compounds, with naphthalene (21.4%) and phenanthrene (21.8%) being dominant. Soil PAH levels from the Pearl River Delta are relatively low (28?C711 ng/g, averaged 192 ng/g) compared to those from urban soils in temperate regions. The mean concentration of ??PAHs generally decrease with increasing distance from the city center, with ??PAHs of paddy soils > crop soil > natural soil. PAHs in the air were measured during a year-round sampling campaign using semipermeable membrane devices, and the transfer of chemicals between the soil and air compartments were estimated. Soil?Cair fugacity quotient calculations showed a highly uncertain equilibrium position of PAHs, with net volatilization of naphthalene and fluorene, whereas net deposition of phenanthrene, fluoranthene, and pyrene, indicating a capacity for the air to supply the soil with more substances.     

Abundances, distribution, and sources of trace metals in Nakaumi–Honjo coastal lagoon sediments, Japan

Bottom sediments from Nakaumi Lagoon and the Honjo Area in southwest Japan were analyzed to determine their geochemical compositions and to assess potential impacts by comparison with sediment quality guidelines. Present-day water quality was also assessed. Results showed that the water quality of Nakaumi Lagoon and the Honjo area contrasts between their upper and lower parts. Average abundances of As, Pb, Zn, Cu, Ni, and Cr in the Nakaumi sediments were 12, 25, 135, 32, 21, and 46 ppm, respectively, compared to 10, 24, 110, 26, 20, and 38 ppm in the Honjo area. All averages are greater than those of the upper continental crust. The elevated metal concentrations are probably related to the fine-grained nature of the sediments, reducing bottom conditions produced by abundant organic matter and possibly minor non-point anthropogenic sources. Trace metal contents are strongly correlated with Fe₂O₃, suggesting that Fe oxides play a role in controlling abundances. Metal concentrations exceed the NYSDEC lowest effect level and CCME interim sediment quality guidelines that indicate moderate impact on aquatic organisms. Average abundances of As and Zn are comparable to the Coastal Ocean Sediment Database threshold, whereas maximum concentrations exceed that value, indicating that the concentrations of these metals are potentially toxic. These enrichments suggest that regular monitoring may be desirable even where no point sources of metal pollution exist.     

Levels of Heavy Metals in Karelian Wildlife, 1989–91

The levels of mercury, cadmium, lead, copper, nickel, zinc and iron were determined in samples of liver, kidney, skeletal muscle, heart, lungs and hair of moose (N = 67), reindeer (N = 45), brown bear (N = 18), wild boar (N = 10) and squirrel (N = 18) shot in Karelia from 1989 to 1991 during regular hunting. The highest heavy-metal concentrations were found in livers, kidney, lungs and hair samples. The samples of muscle contained lowest levels of these elements. The tissues of moose, reindeer and brown bear were contaminated with heavy metals to a greatest extent. Lowest levels of toxicants were recorded in wild boar. Results indicate a widespread presence of heavy metal in the environment and in wildlife, which may be linked to acid precipitation. There was no evidence of these elements accumulated to toxic levels, but Karelian public have been informed that the eating of moose liver and kidney would probably result in their exceeding WHO standard weekly intake limit for cadmium.     

Environmental contaminants in male river otters from Oregon and Washington, USA, 1994–1999

This study reports hepatic concentrations and distribution patterns of select metals, organochlorine pesticides (OCs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in 180 male river otters (Lontra canadensis) collected from Oregon and Washington, 1994-1999. Seven regional locations of western Oregon and Washington were delineated based on associations with major population centers, industry or agriculture. Cadmium (Cd) was not found above 0.5 microg g(-1), dry weight (dw) in juveniles, but increased with age in adults though concentrations were generally low (nd-1.18 microg g(-1), dw). Regional geometric means for total mercury (THg) ranged from 3.63 to 8.05 microg g(-1), dw in juveniles and 3.46-12.6 microg g(-1) (dw) in adults. The highest THg concentration was 148 microg g(-1), dw from an apparently healthy adult male from the Olympic Peninsula of Washington. Although THg increased with age in adult otters, the occurrence of the more toxic form methylmercury (MeHg) was not evaluated. Mean OC and PCB concentrations reported in this study declined dramatically from those reported in 1978-1979 from the lower Columbia River. Organochlorine pesticide and metabolite means for both juvenile and adult river otter males were all below 100 microg kg(-1), wet weight (ww), with only DDE, DDD and HCB having individual concentrations exceeding 500 microg kg(-1), ww. Mean SigmaPCB concentrations in both juvenile and adult male otters were below 1 microg g(-1) for all regional locations. Mean juvenile and adult concentrations of non-ortho substituted PCBs, PCDDs and PCDFs were in the low ng kg(-1) for all locations studied.     

Soil respiration,labile carbon pools,and enzyme activities as affected by tillage practices in a tropical rice–maize–cowpea cropping system

In order to identify the viable option of tillage practices in rice–maize–cowpea cropping system that could cut down soil carbon dioxide (CO₂) emission, sustain grain yield, and maintain better soil quality in tropical low land rice ecology soil respiration in terms of CO₂ emission, labile carbon (C) pools, water-stable aggregate C fractions, and enzymatic activities were investigated in a sandy clay loam soil. Soil respiration is the major pathway of gaseous C efflux from terrestrial systems and acts as an important index of ecosystem functioning. The CO₂–C emissions were quantified in between plants and rows throughout the year in rice–maize–cowpea cropping sequence both under conventional tillage (CT) and minimum tillage (MT) practices along with soil moisture and temperature. The CO₂–C emissions, as a whole, were 24 % higher in between plants than in rows, and were in the range of 23.4–78.1, 37.1–128.1, and 28.6–101.2 mg m^?2 h^?1 under CT and 10.7–60.3, 17.3–99.1, and 17.2–79.1 mg m^?2 h^?1 under MT in rice, maize, and cowpea, respectively. The CO₂–C emission was found highest under maize (44 %) followed by rice (33 %) and cowpea (23 %) irrespective of CT and MT practices. In CT system, the CO₂–C emission increased significantly by 37.1 % with respect to MT on cumulative annual basis including fallow. The CO₂–C emission per unit yield was at par in rice and cowpea signifying the beneficial effect of MT in maintaining soil quality and reduction of CO₂ emission. The microbial biomass C (MBC), readily mineralizable C (RMC), water-soluble C (WSC), and permanganate-oxidizable C (PMOC) were 19.4, 20.4, 39.5, and 15.1 % higher under MT than CT. The C contents in soil aggregate fraction were significantly higher in MT than CT. Soil enzymatic activities like, dehydrogenase, fluorescein diacetate, and β-glucosidase were significantly higher by 13.8, 15.4, and 27.4 % under MT compared to CT. The soil labile C pools, enzymatic activities, and heterotrophic microbial populations were in the order of maize?>?cowpea?>?rice, irrespective of the tillage treatments. Environmental sustainability point of view, minimum tillage practices in rice–maize–cowpea cropping system in tropical low land soil could be adopted to minimize CO₂–C emission, sustain yield, and maintain soil health.     

Hydrogeochemistry and water quality assessment of the Kor–Sivand Basin, Fars province, Iran

In order to assess the quality and suitability of waters in the Kor-Sivand river basin, 60 water samples from the Kor river and 90 water samples from wells in the basin were studied. Assessments were based on Piper's and Gibbs' diagrams for water quality, Food and Agricultural Organization's (FAO) guidelines, and US Salinity Laboratory diagram for water suitability. The results showed that the river water is of Ca-HCO(3) type, while well water is of Ca-Cl and Na-Cl type. Based on Gibbs' diagram, the source of soluble ions in the river water samples is the weathering of stones over which water flows, while evaporation was found to be the dominant process in the ion concentration of the well samples. According to the FAO Guidelines, the salinity of surface water for irrigation did not cause great restrictions; however, many of these waters could create potential permeability problems. In the groundwater samples, a high salt concentration is more important than the infiltration problem. Mg hazard values at some sites limit its use for agricultural purposes. One third of the river water samples and two thirds of well waters had more than 50% magnesium. Saturation indices showed that 94% of the analyzed water samples are supersaturated with calcite, aragonite, and dolomite. Based on the US Salinity Laboratory diagram, river water samples were classified as C(2)S(1) and C(3)S(1), while C(4)S(3), C(4)S(4), C(2)S(1), and C(3)S(1) were the most dominant classes in well samples. Some management practices necessary for sustainable development of water resources in the study area were discussed briefly, including appropriate selection of crops, adequate drainage, leaching, blending and cyclic use of saline water, proper irrigation method, and addition of soil amendment.