Paper-based diffusive gradients in thin films technique coupled to energy dispersive X-ray fluorescence spectrometry for the determination of labile Mn, Co, Ni, Cu, Zn and Pb in river water

The diffusive gradients in thin films (DGT) technique has shown enormous potential for labile metal monitoring in fresh water due to the preconcentration, time-integrated, matrix interference removal and speciation analytical features. In this work, the coupling of energy dispersive X-ray fluorescence (EDXRF) with paper-based DGT devices was evaluated for the direct determination of Mn, Co. Ni, Cu, Zn and Pb in fresh water. The DGT samplers were assembled with cellulose (Whatman 3 MM chromatography paper) as the diffusion layer and a cellulose phosphate ion exchange membrane (Whatman P 81 paper) as the binding agent. The diffusion coefficients of the analytes on 3 MM chromatography paper were calculated by deploying the DGT samplers in synthetic solutions containing 500 mu g L-1 of Mn. Co, Ni, Cu, Zn and Pb (4 L at pH 5.5 and ionic strength at 0.05 mol L-1). After retrieval, the DGT units were disassembled and the P81 papers were dried and analysed by EDXRF directly. The 3 MM chromatographic paper diffusion coefficients of the analytes ranged from 1.67 to 1.87 x 10(-6) cm(2) s(-1). The metal retention and phosphate group homogeneities on the P81 membrane was studied by a spot analysis with a diameter of 1 mm. The proposed approach (DGT-EDXRF coupling) was applied to determine the analytes at five sampling sites (48 h in situ deployment) on the Piracicaba river basin, and the results (labile fraction) were compared with 0.45 mu m dissolved fractions determined by synchrotron radiation-excited total reflection X-ray fluorescence (SR-TXRF). The limits of detection of DGT-EDXRF coupling for the analytes (from 7.5 to 26 mu g L-1) were similar to those obtained by the sensitive SR-TXRF technique (3.8 to 9.1 mu g L-1). (C) 2012 Elsevier B.V. All rights reserved.

Measurement of airborne gunshot particles in a ballistics laboratory by sector field inductively coupled plasma mass spectrometry

The present study aimed determines lead (Pb), antimony (Sb) and barium (Ba) as the major elements present in GSR in the environmental air of the Ballistics Laboratory of the Sao Paulo Criminalistics Institute (I.C.-S.P.), Sao Paulo, SP, Brazil. Micro environmental monitors (mini samplers) were located at selected places. The PM2.5 fraction of this airborne was collected in, previously weighted filters, and analyzed by sector field inductively coupled plasma mass spectrometer (SF-HR-ICP-MS). The higher values of the airborne lead, antimony and barium, were found at the firing range (lead (Pb): 58.9 mu g/m(3); barium (Ba): 6.9 mu g/m(3); antimony (Sb): 7.3 mu g/m(3)). The mean value of the airborne in this room during 6 monitored days was Pb: 23.1 mu g/m(3); Ba: 2.2 mu g/m(3); Sb: 1.5 mu g/m(3). In the water tank room, the air did not show levels above the limits of concern. In general the airborne lead changed from day to day, but the barium and antimony remained constant. Despite of that, the obtained values suggest that the workers may be exposed to airborne lead concentration that can result in an unhealthy environment and could increase the risk of chronic intoxication. (C) 2011 Elsevier Ireland Ltd. All rights reserved.

Analisi dei cantieri di Cippatura in merito ad aspetti operativi e di salvaguardia degli operatori

La cippatura è un processo produttivo fondamentale nella trasformazione della materia prima forestale in biomassa combustibile che coinvolgerà un numero sempre più crescente di operatori. Scopo dello studio è stato quantificare la produttività e il consumo di combustibile in 16 cantieri di cippatura e determinare i livelli di esposizione alla polvere di legno degli addetti alla cippatura, in funzione di condizioni operative differenti. Sono state identificate due tipologie di cantiere: uno industriale, con cippatrici di grossa taglia (300-400kW) dotate di cabina, e uno semi-industriale con cippatrici di piccola-media taglia (100-150kW) prive di cabina. In tutti i cantieri sono stati misurati i tempi di lavoro, i consumi di combustibile, l’esposizione alla polvere di legno e sono stati raccolti dei campioni di cippato per l’analisi qualitativa. Il cantiere industriale ha raggiunto una produttività media oraria di 25 Mg tal quali, ed è risultato 5 volte più produttivo di quello semi-industriale, che ha raggiunto una produttività media oraria di 5 Mg. Ipotizzando un utilizzo massimo annuo di 1500 ore, il cantiere semi-industriale raggiunge una produzione annua di 7.410 Mg, mentre quello industriale di 37.605 Mg. Il consumo specifico di gasolio (L per Mg di cippato) è risultato molto minore per il cantiere industriale, che consuma in media quasi la metà di quello semi-industriale. Riguardo all’esposizione degli operatori alla polvere di legno, tutti i campioni hanno riportato valori di esposizione inferiori a 5 mg/m3 (limite di legge previsto dal D.Lgs. 81/08). Nei cantieri semi-industriali il valore medio di esposizione è risultato di 1,35 mg/m3, con un valore massimo di 3,66 mg/m3. Nei cantieri industriali si è riscontrato che la cabina riduce drasticamente l’esposizione alle polveri di legno. I valori medi misurati all’esterno della cabina sono stati di 0,90 mg/m3 mentre quelli all’interno della cabina sono risultati pari a 0,20 mg/m3.

Application of innovative methods of source apportionment in air contamination assessment

In this work, new tools in atmospheric pollutant sampling and analysis were applied in order to go deeper in source apportionment study. The project was developed mainly by the study of atmospheric emission sources in a suburban area influenced by a municipal solid waste incinerator (MSWI), a medium-sized coastal tourist town and a motorway. Two main research lines were followed. For what concerns the first line, the potentiality of the use of PM samplers coupled with a wind select sensor was assessed. Results showed that they may be a valid support in source apportionment studies. However, meteorological and territorial conditions could strongly affect the results. Moreover, new markers were investigated, particularly focusing on the processes of biomass burning. OC revealed a good biomass combustion process indicator, as well as all determined organic compounds. Among metals, lead and aluminium are well related to the biomass combustion. Surprisingly PM was not enriched of potassium during bonfire event. The second research line consists on the application of Positive Matrix factorization (PMF), a new statistical tool in data analysis. This new technique was applied to datasets which refer to different time resolution data. PMF application to atmospheric deposition fluxes identified six main sources affecting the area. The incinerator’s relative contribution seemed to be negligible. PMF analysis was then applied to PM2.5 collected with samplers coupled with a wind select sensor. The higher number of determined environmental indicators allowed to obtain more detailed results on the sources affecting the area. Vehicular traffic revealed the source of greatest concern for the study area. Also in this case, incinerator’s relative contribution seemed to be negligible. Finally, the application of PMF analysis to hourly aerosol data demonstrated that the higher the temporal resolution of the data was, the more the source profiles were close to the real one.

Caratterizzazione idrogeologica dell'acquifero presente all'interno di cordoni litoranei antropizzati: casi studio di Marina Romea e Porto Corsini

Secondo l'Agenzia Europea dell'Ambiente una delle principali minacce per le risorse di acqua dolce della zone costiere italiane è l’intrusione salina. L’obiettivo di questa tesi magistrale è la caratterizzazione idrogeologica di una frazione dell’acquifero freatico costiero situato in due differenti corpi dunosi. L’indagine proseguita per cinque mesi ha evidenziano differenze tra un’area sottoposta a forte pressione antropica (Marina Romea) e un’area che mostra un relativo sviluppo naturale del sistema spiaggia-duna (Porto Corsini). La tecnica di campionamento utilizzata è il sistema a minifiltri (multi level samplers), metodologia innovativa che garantisce tempistiche di monitoraggio rapide e una campionatura multi-livello puntuale e precisa. La campagna di monitoraggio ha coinvolto misure di freatimetria, conduttività elettrica e analisi chimiche delle acque che hanno portato ad una loro classificazione geo-chimica. Dai risultati si evidenzia che l’acquifero è molto salinizzato, gli strati d’acqua dolce sono isolati in lenti superficiali e i tipi di acque presenti sono dominati da ioni sodio e cloro. Tra i due siti il più vulnerabile risulta essere Marina Romea per molti fattori: l’erosione costiera che assottiglia la fascia dunale adibita alla ricarica di acqua dolce, un’estensione spaziale della duna minore rispetto a Porto Corsini, la presenza di infrastrutture turistiche che hanno frazionato la duna, la vicinanza al canale di drenaggio che causa la risalita delle acque profonde saline, la presenza di specie arboree idro-esigenti che attingono e quindi assottigliano le lenti d’acqua dolce. Si propone di migliorare la qualità dell’acqua sotterranea con una migliore gestione del canale di drenaggio, sostituendo alcuni esemplari di pinacee con specie arbustive tipiche degli ambienti dunosi ed infine imponendo misure per il risparmio idrico durante la stagione turistica.

Cladophora, mass transport, and the nearshore phosphorus shunt

Excessive Cladophora growth in the Great Lakes has led to beach fouling and the temporary closure of nuclear power plants and has been associated with avian botulism and the persistence of human pathogens. As the growth-limiting nutrient for Cladophora, phosphorus is the appropriate target for management efforts. Dreissenids (zebra and quagga mussels) have the ability to capture particulate phase phosphorus (otherwise unavailable to Cladophora) and release it in a soluble, available form. The significance of this potential nutrient source is, in part, influenced by the interplay between phosphorus flux from the mussel bed and turbulent mixing in establishing the phosphorus levels to which Cladophora is exposed. It is hypothesized that under quiescent conditions phosphorus will accumulate near the sediment-water interface, setting up vertical phosphorus gradients and favorable conditions for resource delivery to Cladophora. These gradients would be eliminated under conditions of wind mixing, reducing the significance of the dreissenid-mediated nutrient contribution. Soluble reactive phosphorus (SRP) levels were monitored over dreissenid beds (densities on the order of 350•m-2 and 3000∙m-2) at a site 8 m deep in Lake Michigan. Monitoring was based on the deployment of Modified Hesslein Samplers which collected samples for SRP analysis over a distance of 34 cm above the bottom in 2.5 cm intervals. Deployment intervals were established to capture a wind regime (calm, windy) that persisted for an interval consistent with the sampler equilibration time of 7 hours. Results indicate that increased mussel density leads to an increased concentration boundary layer; increased wind speed leads to entrainment of the concentration boundary layer; and increased duration of quiescent periods leads to an increased concentration boundary layer. This concentration boundary layer is of ecological significance and forms in the region inhabited by Cladophora

Bioavailability of pharmaceuticals in waters close to wastewater treatment plants: use of fish bile for exposure assessment

Pharmaceuticals are ubiquitous in surface waters as a consequence of discharges from municipal wastewater treatment plants. However, few studies have assessed the bioavailability of pharmaceuticals to fish in natural waters. In the present study, passive samplers and rainbow trout were experimentally deployed next to three municipal wastewater treatment plants in Finland to evaluate the degree of animal exposure. Pharmaceuticals from several therapeutic classes (in total 15) were analyzed by liquid chromatography-tandem mass spectrometry in extracts of passive samplers and in bile and blood plasma of rainbow trout held at polluted sites for 10 d. Each approach indicated the highest exposure near wastewater treatment plant A and the lowest near that of plant C. Diclofenac, naproxen, and ibuprofen were found in rainbow trout, and their concentrations in bile were 10 to 400 times higher than in plasma. The phase I metabolite hydroxydiclofenac was also detected in bile. Hence, bile proved to be an excellent sample matrix for the exposure assessment of fish. Most of the monitored pharmaceuticals were found in passive samplers, implying that they may overestimate the actual exposure of fish in receiving waters. Two biomarkers, hepatic vitellogenin and cytochrome P4501A, did not reveal clear effects on fish, although a small induction of vitellogenin mRNA was observed in trout caged near wastewater treatment plants B and C.

Assessment of the performance of 3m 3500 organic vapor monitors over extended sampling durations

The purpose of this study was to assess the accuracy and precision of airborne volatile organic compound (VOC) concentrations measured using passive air samplers (3M 3500 organic vapor monitors) over extended sampling durations (9 and 15 days). A total of forty-five organic vapor monitor samples were collected at a State of Texas air monitoring site during two different sampling periods (July/August and November 2008). The results of this study indicate that for most of the tested compounds, there was no significant difference between long-term (9 or 15 days) sample concentrations and the means of parallel consecutive short-term (3 days) sample concentrations. Biases of 9 or 15-day measurements vs. consecutive 3-day measurements showed considerable variability. Those compounds that had percent bias values of <10% are suggested as acceptable for long-term sampling (9 and 15 days). Of the twenty-one compounds examined, 10 compounds are classified as acceptable for long-term sampling; these include m,p-xylene, 1,2,4-trimethylbenzene, n-hexane, ethylbenzene, benzene, toluene, o-xylene, d-limonene, dimethylpentane and methyl tertbutyl ether. The ratio of sampling procedure variability relative to variability within days was approximately 1.89 for both sampling periods for the 3-day vs. 9-day comparisons and approximately 2.19 for both sampling periods for the 3-day vs. 15-day comparisons. Considerably higher concentrations of most VOCs were measured during the November sampling period compared to the July/August period. These differences may be a result of varying meteorological conditions during these two time periods, e.g., the differences in wind direction, and wind speed. Further studies are suggested to further evaluate the accuracy and precision of 3M 3500 organic vapor monitors over extended sampling durations. ^

Nitrogen dioxide exposures among a selected group of residents of substandard housing in Houston, Texas

Nitrogen dioxide (NO$\sb2)$ levels in sixteen substandard houses located in Houston, Texas were examined. The classification of the houses as substandard was based on an assessment of structural integrity which would affect air exchange rates. In these homes, unvented gas space heaters were operated as the primary source of heat.^ The Ogawa passive sampling device was used to measure NO$\sb2$ concentrations over 24 to 48-hour periods during generally cold weather. A sampler was placed in the kitchen and bedroom of each house. The female head of household was asked to wear a monitor during area monitoring to assess her personal exposure. Outdoor levels of NO$\sb2$ were also measured.^ Mean (standard deviation) levels of kitchen, bedroom and personal exposures were 280 (125) ppb, 256 (155) ppb and 164 (102) ppb, respectively. Additional short-term ($<$24 hours) samples were measured in three houses. The mean level of NO$\sb2$ measured outdoors was 51 ppb over the course of the study.^ The measurements obtained with the Ogawa sampler were compared to those levels obtained using a reference method (chemiluminescence). Outdoor levels measured with the diffusion samplers were 48% higher.^ These results suggest that wintertime NO$\sb2$ levels within substandard houses using gas appliances for heating and cooking are extremely elevated. Further work is needed to investigate the prevalence of possible health effects associated with these exposures. ^

A QUANTITATIVE INVESTIGATION OF SOURCE AND ELEMENTAL COMPOSITION OF INDOOR AND OUTDOOR FINE PARTICULATE AIR POLLUTION IN HOUSTON (TEXAS)

An investigation was undertaken to determine the chemical characterization of inhalable particulate matter in the Houston area, with special emphasis on source identification and apportionment of outdoor and indoor atmospheric aerosols using multivariate statistical analyses.^ Fine (<2.5 (mu)m) particle aerosol samples were collected by means of dichotomous samplers at two fixed site (Clear Lake and Sunnyside) ambient monitoring stations and one mobile monitoring van in the Houston area during June-October 1981 as part of the Houston Asthma Study. The mobile van allowed particulate sampling to take place both inside and outside of twelve homes.^ The samples collected for 12-h sampling on a 7 AM-7 PM and 7 PM-7 AM (CDT) schedule were analyzed for mass, trace elements, and two anions. Mass was determined gravimetrically. An energy-dispersive X-ray fluorescence (XRF) spectrometer was used for determination of elemental composition. Ion chromatography (IC) was used to determine sulfate and nitrate.^ Average chemical compositions of fine aerosol at each site were presented. Sulfate was found to be the largest single component in the fine fraction mass, comprising approximately 30% of the fine mass outdoors and 12% indoors, respectively.^ Principal components analysis (PCA) was applied to identify sources of aerosols and to assess the role of meteorological factors on the variation in particulate samples. The results suggested that meteorological parameters were not associated with sources of aerosol samples collected at these Houston sites.^ Source factor contributions to fine mass were calculated using a combination of PCA and stepwise multivariate regression analysis. It was found that much of the total fine mass was apparently contributed by sulfate-related aerosols. The average contributions to the fine mass coming from the sulfate-related aerosols were 56% of the Houston outdoor ambient fine particulate matter and 26% of the indoor fine particulate matter.^ Characterization of indoor aerosol in residential environments was compared with the results for outdoor aerosols. It was suggested that much of the indoor aerosol may be due to outdoor sources, but there may be important contributions from common indoor sources in the home environment such as smoking and gas cooking. ^

A STUDY OF DIVERSITY AND COMMUNITY COMPARISON INDICES BY BIOASSAY OF COPPER USING COLONIZED BENTHIC MACROINVERTEBRATES

A community bioassay of copper was performed using benthic macroinvertebrates colonized on multiplate substrate samplers. Five copper concentrations ranging from 0.080-2.20 mg/l total copper were administered to five artificial streams by a Mount and Brungs proportional dilutor. Free copper ion as Cu('++) ranged from .002-.053 mg/l. A sixth stream received no copper and served as a control. Substrates were sampled at days 0, 14, and 28, and the results were used to compare 13 indices used or proposed to assess aquatic environmental impact. Sensitivity of the indices to changes in communities with respect to concentration and time was the basis for the comparison.^ Results indicated that all of the 8 diversity or richness indices tested gave approximately the same result (with the exception of number of species); they increased over the first 2-3 concentrations, then declined. Included among these was the Shannon index which gave false positive results, i.e., it increased, indicating enrichment, when in fact perturbation had occurred. This result was due to the disproportionate effect on the most abundant taxa, which caused a more even distribution of individuals among species. Number of species and individuals declined with increased concentration and time, with only one exception in the case of species, indicating perturbation.^ Results of five community comparison indices were varied at day 14 but by day 28 the results indicated a clear, nearly monotonic, trend due to copper impact. It was assumed that day 28 observations, though probably still changing, were nearer stability than at day 14 and therefore more representative of natural conditions. The changes in community comparison indices showed good agreement at 28 days and reflected the general decline in species and individuals. No single community comparison index could be set apart as superior to the others. ^

Chamber evaluation of a personal organic vapor dosimeter at ppb concentrations of VOCs, varying temperatures and humidities with 24 -hour exposures

An exposure system was constructed to evaluate the performance of a personal organic vapor dosimeter (3520 OVM) at ppb concentrations of nine selected target volatile organic compounds (VOCs). These concentration levels are generally encountered in community air environments, both indoor and outdoor. It was demonstrated that the chamber system could provide closely-controlled conditions of VOC concentrations, temperature and relative humidity (RH) required for the experiments. The target experimental conditions included combinations of three VOC concentrations (10, 20 and 200 $\rm\mu g/m\sp3),$ three temperatures (10, 25 and 40$\sp\circ$C) and three RHs (12, 50 and 90% RH), leading to a total of 27 exposure conditions. No backgrounds of target VOCs were found in the exposure chamber system. In the exposure chamber, the variation of the temperature was controlled within $\pm$1$\sp\circ$C, and the variation of RH was controlled within $\pm$1.5% at 12% RH, $\pm$2% at 50% RH and $\pm$3% at 90% RH. High-emission permeation tubes were utilized to generate the target VOCs. Various patterns of the permeation rates were observed over time. The lifetimes and permeation rates of the tubes differed by compound, length of the tube and manufacturer. By carefully selecting the source and length of the tubes, and closely monitoring tube weight loss over time, the permeation tubes can be used for delivering low and stable concentrations of VOCs during multiple days.^ The results of this study indicate that the performance of the 3520 OVM is compound-specific and depends on concentration, temperature and humidity. With the exception of 1,3-butadiene under most conditions, and styrene and methylene chloride at very high relative humidities, recoveries were generally within $\pm$25% of theory, indicating that the 3520 OVM can be effectively used over the range of concentrations and environmental conditions tested with a 24-hour sampling period. Increasing humidities resulted in increasing negative bias from full recovery. Reverse diffusion conducted at 200 $\rm\mu g/m\sp3$ and five temperature/humidity combinations indicated severe diffusion losses only for 1,3-butadiene, methylene chloride and styrene under increased humidity. Overall, the results of this study do not support the need to employ diffusion samplers with backup sections for the exposure conditions tested. ^

Inorganic carbon and geochemistry measurements from landfast sea ice in Resolute Passage, Nunavut, Canada, as part of the Arctic-ICE project, May - June 2010

We conducted a six-week investigation of the sea ice inorganic carbon system during the winter-spring transition in the Canadian Arctic Archipelago. Samples for the determination of sea ice geochemistry were collected in conjunction with physical and biological parameters as part of the 2010 Arctic-ICE (Arctic - Ice-Covered Ecosystem in a Rapidly Changing Environment) program, a sea ice-based process study in Resolute Passage, Nunavut. The goal of Arctic-ICE was to determine the physical-biological processes controlling the timing of primary production in Arctic landfast sea ice and to better understand the influence of these processes on the drawdown and release of climatically active gases. The field study was conducted from 1 May to 21 June, 2010.

Stable isotope geochemistry of pore waters and marine sediments from the New Jersey shelf: Methane formation and fluid origin

Interstitial water and sediment samples of the Integrated Ocean Drilling Program (IODP) expedition 313 "New Jersey Shallow Shelf" were analyzed for chemical composition and stable isotope ratios. A total of 222 water samples were collected from the cores by Rhizon samplers and squeezing of fresh core material. Water was analyzed for its stable oxygen and hydrogen isotope geochemistry (d2H and d18O) at sites M0027A and M0029A, and the carbon isotope composition of the dissolved inorganic carbon (d13CDIC) (all sites). In addition, organic material (Corg) and inorganic carbonates from sediments were analyzed for their carbon ratios (d13Corg and d13Ccarb), and in case of the carbonates also for oxygen (d18Ocarb). Carbon isotopes were also analyzed in samples containing enough methane gas (d13Cmeth). Pore fluids from site M0027A were analyzed for the sulfur isotope composition of dissolved sulfate (d34S). The combination of isotope analyses of all phases (interstitial water, sediment, and gas) with pore water chemistry is expected to enable a better understanding of processes in the sediment and will help to identify the origin of fluids under the New Jersey shelf.

On the fine structure of oxygen distribution in surface water layers in the area between Iceland and Faroe Islands

During the international "Overflow-Expedition'' 1973 on R.V. "Meteor" oxygen concentrations in surface layers were measured in order to determine the oxygen gradients within the first two meters and to add some informations to the mechanisms of oxygen exchange at the air-sea interface. These investigations may be interesting also with regard to longterm- observations of the oxygen distribution in the Atlantic, especially the problem of the A.O.U. (apparent oxygen utilization) determination. To measure oxygen gradients a special sampler was built which is able to take water samples each 20 cm of the first 2 meters. These data were supplemented by further samples down to 150 m, taken by conventional water samplers, from which samples were also taken to measure N2/O2-relations. By comparing these relations with theoretical relations in air-saturated water the influence of biological production and consumption on the oxygen contents in water could be estimated. A simple glass apparatus was built to extract gas from the water samples, and hereafter the N2/O2-relations were determined by mass spectrometry. Most distributions of the oxygen anomaly show a negative oxygen balance which varies largely, probably due to strong mixing processes in the Iceland-Faroe ridge area. The distribution of surface oxygen saturation values are of two different types. The values of the stations 260, 262 and 270 stem from mixed water and show homogeneous supersaturations, as can be found instantly when whitecaps appear. The values of 9 other stations are from water, sampled during calm periods which has been mixed and supersaturated before. They show a decreasing oxygen saturation towards the sea surface and often undersaturation in the upper decimeters up to 98 % and even 91 %. So at the air-sea interface even less initial oxygen saturation than 100 % can be found after supersaturation during heavy weather periods.