Brazilian Oil Spills Chemical Characterization—Case Studies

In the last decade, PETROBRAS has experienced some significant oil spills cases and the PETROBRAS Research Center has played an important role in the company emergency response program by characterizing the spilled oil, monitoring the affected ecosystem, determining the fate of the oil in the environment, and, subsequently, helping the company in assessing the environmental damage. This paper presents the use of advanced chemical analytical techniques (GC/FID, P&T/GC/PID and GC/MS) in some Brazilian oil spill studies in order to determine fractions and individual petroleum hydrocarbons in different matrices such as water, groundwater, sediment, sand, fish and the spilled oil itself. The spill studies encompassed crude and fuel oil releases on land and coastal ecosystems, related to the incidents in Guanabara Bay (Rio de Janeiro), Barigui and Iguassu Rivers (Parana) and Sao Sebastiao Channel (Sao Paulo). Total petroleum hydrocarbons (TPH), n -alkanes, isoprenoids, unresolved complex mixtures (UCM), volatile monoaromatic compounds—benzene, toluene, ethylbenzene and xylenes (BTEX), parent and alkylated homologues polycyclic aromatic hydrocarbons (PAH), and terpanes and steranes were characterized for determining correlation to the spilled oil and other known oil sources and environmental assessment. Some of the acute ecotoxicity data for water and sediment samples is also presented.     

Chemical species’ contributions to the upper extremes of aerosol fine mass

Frequency distributions of the major chemical components of aerosol fine mass are shown to illustrate the respective species’ contributions to the range of observed fine particle mass concentration. The magnitude of a species’ contribution to the upper extremes of aerosol fine mass is relevant to control scenarios that seek to improve worst day fine particle conditions, or in many cases worst day visibility. We summarize the relative contributions of fine particle sulfate, nitrate, carbon, and soil plus sea salt to the upper extremes of aerosol fine mass based on Interagency Monitoring of PROtected Visual Environments (IMPROVE) data collected at monitoring locations across the United States during 1995 through 1999. The data show that the spatial pattern of a given chemical species’ contribution to the upper extremes of aerosol fine mass is often quite different than at lower fine mass concentrations. In some cases, the monitoring data suggest a casual relationship between specific aerosol source regions and the magnitude in which a species’ contribution to the upper extremes of fine mass is elevated above the contribution to median fine mass concentrations.     

Chemical composition of snowfall in the high Arctic: 1990–1994

From 1990 to 1994 at Alert, Nunavut, Canada, weekly snow samples were collected under low wind conditions to avoid contamination by blowing snow. They were analysed for major ions, Br⁻, and the organic ions methylsulphonate, formate, acetate and propionate. In the Arctic, where annual precipitation is low and blowing snow is common, these observations are unique. On an equivalent weight basis, acids and sea salt in snowfall are mixed approximately equally from December to January but from March to May acids dominate. The acidity of snowfall increases progressively throughout the winter to a May peak of ∼16 μeq l⁻¹. SO₄²⁻, Br⁻, and the organic acids acetate, and propionate peak in snowfall after polar sunrise indicate the influence of enhanced photochemical reactions. The greater enrichment of halides relative to sea salt Na⁺ in snow compared to aerosols indicates that gaseous uptake by snowflakes is important in the removal of these substances from the atmosphere and their deposition on to the Earth's surface. There is a marked difference between the seasonal variation of enrichment of Cl⁻ and Br⁻ in snow. The latter show a marked increase after polar sunrise while the former does not. These results provide valuable baseline information on the ionic content of fresh snowfall to be used in understanding the results of snowpack chemistry and post-depositional process studies conducted in the high Arctic.     

Biological activity and bioavailability of grain bound 14C‐malathion residues in rats

Abstract

Paddy (unmilled rice), milled rice and maize‐bound ¹⁴C residues were prepared using ¹⁴C‐succinate‐labelled malathion at 10 and 152 ppm. After 3 months, the bound residues accounted for 12%, 6.5% and 17.7% of the applied dose in paddy, milled rice and maize respectively in the grains treated at 10 ppm. The corresponding values for the 152 ppm were 16.6%, 8.5% and 18.8%. Rats fed milled rice ‐ bound ¹⁴C‐residues eliminated 61% of the ¹⁴C in the faeces and 28% in the urine. The corresponding percentages for paddy and maize were 72%, 9% and 53%, 41% respectively; indicating that bound residues from milled rice and maize were moderately bioavailable. When rice‐bound malathion residues (0.65 ppm in feed) were administered to rats in a 5 week feeding study, no signs of toxicity were observed. Plasma and RBC cholinesterase activities were slightly inhibited: blood urea nitrogen was significantly elevated in the test animals. Other parameters examined showed no or marginal changes.     

Analysis of Herbicide Krovar I™ by Liquid Chromatography with Atmospheric Pressure Chemical Ionization Mass Spectrometry

Abstract

A simple, very efficient method is presented for routine analysis of herbicide Krovar I? (active components bromacil and diuron) in water and soil samples. Water samples were extracted by liquid–liquid extraction with dichloromethane (DCM) as extraction solvent. For soil samples two different extraction techniques were compared: microwave-assisted solvent extraction and a shaking technique using a platform shaker. Extracts were analyzed by high performance liquid chromatography using a water:methanol gradient. Liquid chromatography was coupled with atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) for quantification of bromacil and diuron. Optimization of the APCI-MS was done by using standards in the flow injection analysis mode (FIA). Method detection limit for liquid samples for bromacil is 0.04 µg L^?1 and for diuron 0.03 µg L^?1. Method detection limit for soil samples is 0.01 µg g^?1 dry weight for both compounds. Results of analysis of field samples of water and soil are also presented.     

Chemical composition of atmospheric precipitation in Czechoslovakia, 1976–1984—I. Monthly samples

The results of chemical analyses of monthly atmospheric precipitation samples from 12 stations within Czechoslovakia are presented. The sampling at the station with the longest record (Hrádek u Pacova, 80 km SE from Prague) covers 9 years. There is no clear regional pattern within the sampled territory, but a spring maximum was observed for most components. For SO₄⁻² and acidity a downward trend was indicated. Statistical analyses show that the important sources of mineralization of precipitation water are (in order of importance): coal combustion; sea spray; terrigenous dust; car exhaust; cement production; “European background” sulphur.     

Chemical Characterization and Source Identification of Polycyclic Aromatic Hydrocarbons in Aerosols Originating from Different Sources

To put waste-to-energy (WTE) in perspective, it is important to see how it measures up environmentally to other power generation utility sources.

This paper compares actual WTE facility emissions with those from fossil fuel combustion utility sources. This comparison is made on an electricity production basis, such as a pound of pollutant per megawatt-hour of net electricity generated, for each power generation source.     

Assessment of Biological and Environmental Phenology at a Landscape Level from 30 Years of Fixed-Date Repeat Photography in Northern Sweden

A 30-year series (1978–2007) of photographic records were analysed to determine changes in lake ice cover, local (low elevation) and montane (high elevation) snow cover and phenological stages of mountain birch (Betula pubescens ssp. czerepanovii) at the Abisko Scientific Research Station, Sweden. In most cases, the photographic-derived data showed no significant difference in phenophase score from manually observed field records from the same period, demonstrating the accuracy and potential of using weekly repeat photography as a quicker, cheaper and more adaptable tool to remotely study phenology in both biological and physical systems. Overall, increases in ambient temperatures coupled with decreases in winter ice and snow cover, and earlier occurrence of birch foliage, signal a reduction in the length of winter, a shift towards earlier springs and an increase in the length of available growing season in the Swedish sub-arctic.     

Atmospheric aerosol over two urban–rural pairs in the southeastern United States: Chemical composition and possible sources

Positive matrix factorization (PMF) was used to infer the sources of PM_2.5 observed at four sites in Georgia and Alabama. One pair of urban and rural sites in each state is used to examine the regional and urban influence on PM_2.5 concentrations in the Southeast. Eight factors were resolved for the two urban sites and seven factors were resolved for the two rural sites. Spatial correlations of factors were investigated using the square of correlation coefficient (R²) calculated from the resolved G factors. Fourier transform was used to define the temporal characteristics of PM_2.5 factors at these sites. Factors were normalized by using aerosol fine mass concentration data through multiple linear regression to obtain the quantitative factor contributions for each resolved factor. Common factors include: (1) secondary sulfate dominated by high concentrations of sulfate and ammonium with a strong seasonal variation peaking in summer; (2) nitrate and the associated ammonium with a seasonal maximum in winter; (3) “coal combustion/other” factor with presence of sulfate, EC, OC, and Se; (4) soil represented by Al, Ca, Fe, K, Si and Ti; and (5) wood smoke with the high concentrations of EC, OC and K. The motor vehicle factor with high concentrations of EC and OC and the presence of some soil dust components is found at the urban sites, but cannot be resolved for the two rural sites. Among the other factors, two similar industry factors are found at the two sites in each state. For the wood smoke factor, different seasonal trends are found between urban and rural sites, suggesting different wood burning patterns between urban and rural regions. For the industry factors, different seasonal variations are also found between urban and rural sites, suggesting that this factor may come from different sources or a common source may impact the two sites differently. Generally, sulfate, soil, and nitrate factors at the four sites showed similar chemical composition profiles and seasonal variation patterns reflecting the regional characteristics of these factors. These regional factors have predominantly low frequency variations while local factors such as coal combustion, motor vehicle, wood smoke, and industry factors have high frequency variations in addition to low frequency variations.     

U.S. National PM2.5 Chemical Speciation Monitoring Networks—CSN and IMPROVE: Description of networks

The U.S. Environmental Protection Agency (EPA) initiated the national PM_2.5 Chemical Speciation Monitoring Network (CSN) in 2000 to support evaluation of long-term trends and to better quantify the impact of sources on particulate matter (PM) concentrations in the size range below 2.5 μm aerodynamic diameter (PM_2.5; fine particles). The network peaked at more than 260 sites in 2005. In response to the 1999 Regional Haze Rule and the need to better understand the regional transport of PM, EPA also augmented the long-existing Interagency Monitoring of Protected Visual Environments (IMPROVE) visibility monitoring network in 2000, adding nearly 100 additional IMPROVE sites in rural Class 1 Areas across the country. Both networks measure the major chemical components of PM_2.5 using historically accepted filter-based methods. Components measured by both networks include major anions, carbonaceous material, and a series of trace elements. CSN also measures ammonium and other cations directly, whereas IMPROVE estimates ammonium assuming complete neutralization of the measured sulfate and nitrate. IMPROVE also measures chloride and nitrite. In general, the field and laboratory approaches used in the two networks are similar; however, there are numerous, often subtle differences in sampling and chemical analysis methods, shipping, and quality control practices. These could potentially affect merging the two data sets when used to understand better the impact of sources on PM concentrations and the regional nature and long-range transport of PM_2.5. This paper describes, for the first time in the peer-reviewed literature, these networks as they have existed since 2000, outlines differences in field and laboratory approaches, provides a summary of the analytical parameters that address data uncertainty, and summarizes major network changes since the inception of CSN.

ImplicationsTwo long-term chemical speciation particle monitoring networks have operated simultaneously in the United States since 2001, when the EPA began regular operations of its PM_2.5 Chemical Speciation Monitoring Network (IMPROVE began in 1988). These networks use similar field sampling and analytical methods, but there are numerous, often subtle differences in equipment and methodologies that can affect the results. This paper describes these networks since 2000 (inception of CSN) and their differences, and summarizes the analytical parameters that address data uncertainty, providing researchers and policymakers with background information they may need (e.g., for 2018 PM_2.5 designation and State Implementation Plan process; McCarthy, 2013) to assess results from each network and decide how these data sets can be mutually employed for enhanced analyses. Changes in CSN and IMPROVE that have occurred over the years also are described.     

Chemical and biological release of 14C‐bound residues from soil treated with 14C‐p,p'‐DDT

Abstract

¹⁴C‐p,p'‐DDT‐bound residues in soil can be released by treatment with concentrated sulphuric acid at ambient temperatures. Within 6 days, about 70% of the bound residues was released. Bound residues released after 9 months incubation with ¹⁴C‐DDT showed the presence of DDT and DDE only while bound residues released after 18 months, contained in addition 13% DDD.

Release of bound ¹⁴C‐residues also occurs readily following inoculation of the soil‐bound residues with fresh soil or with individual microorganisms. Almost complete release of bound residues was observed after incubation for 45 days. The rate of release was rapid during the first two weeks and decreased thereafter. TLC and HPLC analysis showed that the released residues contained DDE (about 80%) and a smaller amount of DDD. The disappearance of DDT from the released residues may be attributed to its microbiological degradation to DDE and DDD, shortly after its release.     

Chemical and morphological characterization of aerosol particles at Mt. Krvavec, Slovenia, during the Eyjafjallajökull Icelandic volcanic eruption

Objective

In this work, continuous and size-segregated aerosol measurements at Mt. Krvavec, Slovenia, during the Eyjafjallajökull volcanic eruption were performed. Based on chemical and morphological characteristics of size-segregated particles, the presence of the volcanic aerosols after long-range transport to Slovenia was to be confirmed.

Results and conclusions

Continuous measurements with the aethalometer and SMPS indicated the suspected volcanic ash plume passing over the sampling site. The aerosols collected by discrete sampling showed a chemical signature similar to the known elemental signature of the Icelandic volcanic ash. Coarse particles showed a composition typical for silicates rich in metals; in many cases also S was present. Morphological analysis showed particles with features indicative of an explosive volcanic eruption, e.g., pumice and pumice shards, glass shards, minerals, evidence of steam condensation, etc. The high sulfate concentration associated with the fine particles resulted in sulfate crystallization within the cascade impactor leading to the formation of large structures resembling a “fern”. Mass size distributions for Fe, Ti, Mn, Ca, Na, and Mg showed one primary peak (for Fe, Mn, and Ti at 2.8 μm; for Ca, Na, and Mg at ca. 4 μm), which supports the fact that most of the particles in the coarse sizes were silicates rich in metals. The size distribution of the water-soluble SO ₄ ^2? showed a maximum peak at 0.75 μm, which also confirms the high sulfate concentration in the fine particles. Chemical and morphological characterization of aerosols collected at Mt. Krvavec indeed confirmed that volcanic ash plume passed over Slovenia.     

Chemical amendment of pig slurry: control of runoff related risks due to episodic rainfall events up to 48 h after application

Losses of phosphorus (P) from soil and slurry during episodic rainfall events can contribute to eutrophication of surface water. However, chemical amendments have the potential to decrease P and suspended solids (SS) losses from land application of slurry. Current legislation attempts to avoid losses to a water body by prohibiting slurry spreading when heavy rainfall is forecast within 48 h. Therefore, in some climatic regions, slurry spreading opportunities may be limited. The current study examined the impact of three time intervals (TIs; 12, 24 and 48 h) between pig slurry application and simulated rainfall with an intensity of 11.0?±?0.59 mm h^?1. Intact grassed soil samples, 1 m long, 0.225 m wide and 0.05 m deep, were placed in runoff boxes and pig slurry or amended pig slurry was applied to the soil surface. The amendments examined were: (1) commercial-grade liquid alum (8 % Al₂O₃) applied at a rate of 0.88:1 [Al/ total phosphorus (TP)], (2) commercial-grade liquid ferric chloride (38 % FeCl₃) applied at a rate of 0.89:1 [Fe/TP] and (3) commercial-grade liquid poly-aluminium chloride (10 % Al₂O₃) applied at a rate of 0.72:1 [Al/TP]. Results showed that an increased TI between slurry application and rainfall led to decreased P and SS losses in runoff, confirming that the prohibition of land-spreading slurry if heavy rain is forecast in the next 48 h is justified. Averaged over the three TIs, the addition of amendment reduced all types of P losses to concentrations significantly different (p?<?0.05) to those from unamended slurry, with no significant difference between treatments. Losses from amended slurry with a TI of 12 h were less than from unamended slurry with a TI of 48 h, indicating that chemical amendment of slurry may be more effective at ameliorating P loss in runoff than current TI-based legislation. Due to the high cost of amendments, their incorporation into existing management practices can only be justified on a targeted basis where inherent soil characteristics deem their usage suitable to receive amended slurry.     

Chemical speciation of individual atmospheric particles using low-Z electron probe X-ray microanalysis:: characterizing “Asian Dust” deposited with rainwater in Seoul,Korea

Chemical speciation of individual microparticles is of much interest in environmental atmospheric chemistry; e.g. the determination of the elemental concentrations in individual atmospheric aerosol particles is important to study the chemical behavior of atmospheric pollution. Recently, an EPMA technique using an X-ray detector equipped with an ultra-thin window, allowing EPMA to determine concentrations of low-Z elements, such as C, N, and O, in individual particles of micrometer size, has been developed. This technique, called low-Z electron probe X-ray microanalysis (low-Z EPMA), is applied to characterize the water-insoluble part of “Asian Dust”, deposited by washout in the form of rainwater during an Asian Dust storm event and collected in Seoul, Korea. In this study, it was demonstrated that the single particle analysis using low-Z EPMA provided detailed information on various types of chemical species in the sample. In addition to aluminosilicates, silicon oxide, iron oxide, and calcium carbonate particles, which are expected to be present, carbonaceous particles are also observed in a significant fraction. This unexpected finding that particle sample originated from an arid area contains significant amount of carbonaceous particles is supported by the investigation of a “China Loess” sample. In addition, we also performed single particle analysis for a local soil sample, in order to check the possible influence from local sources on “Asian Dust”. The characteristics of the local soil particle sample, e.g. the types of aluminosilicate particles and the abdundance of particles with deviating chemical species, are clearly different from “Asian Dust” and “China Loess” samples, whereas those two are similar, implying that the “Asian Dust” sample was not much influenced by local sources.     

Biological effect monitoring in dab (<Emphasis Type="Italic">Limanda limanda</Emphasis>) using gene transcript of CYP1A1 or EROD—a comparison

BACKGROUND, AIM, AND SCOPE: Gene expression analyses with real-time (RT)-polymerase chain reaction (PCR) gains importance in marine monitoring. This new technique has to be compared to the classical approaches like the well known biomarker ethoxyresorufin-O-deethylase (EROD) to test their suitability for monitoring programmes. The goal of the present study is to compare EROD activity and CYP1A1 mRNA expression in the important monitoring fish species dab (Limanda limanda) and to answer the question of whether these parameters reflect the polycyclic aromatic hydrocarbon (PAH) contamination of the fish. Further on, glyceraldehyd-3-phosphate dehydrogenase (GAPDH) was investigated as a potential housekeeping gene. MATERIALS AND METHODS: Female dab were caught in the summer of 2004 in the North Sea and in the Baltic. EROD activity was determined in liver samples by a kinetic fluorimetric assay according to a standard protocol. The gene expression of CYP1A (cytochrome P450 1A) and GAPDH were determined by means of RT-PCR. Results were compared to gonado somatic index and to the concentration of PAH metabolite 1OHPyr (1-hydroxypyrene) analysed in the bile fluids of the fish, respectively. RESULTS: Dab from all stations showed a considerable individual variation in the levels of both CYP1A mRNA and EROD. Highest mean values for CYP1A mRNA and EROD were detected in the northern part of the sampling area. In contrast, the PAH metabolite 1OHPyr was found at the highest concentration in fish caught near the German coast. CYP1A mRNA and EROD showed only a minor but significant correlation (r = 0.32, p < 0.05, n = 123). 1OHPyr in bile correlated significantly (p < 0.05) with the amount of GAPDH mRNA content in the liver. DISCUSSION: The significant but low correlation of CYP1A mRNA and EROD activity on an individual basis illustrates that these two parameters are apparently not closely linked. However, maximum EROD values correspond with maximum CYP1A mRNA concentrations when station means are regarded. Because EROD and CYP1A mRNA in dab follow different physiological principles, their application will lead to related but not identical monitoring results. This should be taken into account when future marine monitoring programmes are designed. The results also indicate that PAH are not the crucial factor for CYP1A and EROD levels in dab from the off-shore areas in the North Sea. This is remarkable because the PAH metabolism is known to be CYP1A-dependent and the widely used biomarker EROD has been recommended for monitoring PAH-related effects in fish from the North Sea. Due to a correlation between GAPDH and 1OHPyr, GAPDH was not suitable as housekeeping gene for dab. CONCLUSIONS: Neither the results from EROD nor from CYP1A1 mRNA measurements in dab reflected their exposure to PAH as measured by the PAH metabolite 1OHPyr. Thus, the question arises of whether EROD or CYP1A mRNA is a suitable biomarker at all to indicate PAH exposure in dab from the open North Sea. RECOMMENDATIONS AND PERSPECTIVES: For future biological effect monitoring, it is advisable to measure more and predominately independent parameters by RT-PCR and to incorporate more components of the detoxification system.     

Investigation on the Chemical Structure of Nonextractable Residues of the Fungicide Cyprodinil in Spring Wheat Using 13C-C1-Phenyl-Cyprodinil on 13C-Depleted Plants—An Alternative Approach to Investigate Nonextractable Residues

Abstract

¹³C-labelled cyprodinil was applied on ¹³C-depleted wheat plants with 27-fold field application rate. A control experiment applying same amounts of ¹⁴C-cyprodinil showed that main portions of the residues were detected in the cellulose (15% NER), hemicellulose (28.3% NER), and lignin fraction (23.3% NER). 16.7% were detected in water soluble polymers, 6% in both, pectin and protein fraction, and 4% in the starch containing fraction. Free cyprodinil was detectable by TLC in all fractions except lignin. A direct characterization of the residues in vivo by CP-MAS was not successful. Cell wall fractions were further analysed by liquid state NMR to determine the structure of the mobilized highly polymer/polar residues: Within lignin, where most of the residues were located at field application rate, neither intact cyprodinil nor its metabolites could not be detected. The ¹³C-label introduced was probably incorporated in the polymer as natural lignin monomers and thus are not considered as bound residues according to IUPAC definition.