Computer Analysis of the California Cycle

The current trend toward greater instrumentation in analysis of automobile exhaust gases is sure to increase in future years. This will come about as a result of increased activity to find a solution to air pollution problems resulting from automobile exhaust gases. Owing to the complex driving cycle needed to evaluate vehicle emission, considerable time has been required to analyze and interpret the records from any run. To alleviate this analytic problem, an automatic data logger was obtained that records on magnetic tape the signal from a number of analytical instruments each second (in binary coded decimal form). These records are then analyzed on a computer to give integrated and averaged results over the specified driving cycle. There is no longer any need for manual evaluation of the data. In addition to the standard analyses already mentioned, the use of the data logger permits a much more complete analysis of what is happening in a vehicle. For example, the analytical instruments used include an oxygen analyzer in addition to carbon dioxide, carbon monoxide, and hydrocarbons. With these measurements the air-fuel ratio of any or all driving conditions can be calculated.     

A Comparison of Phenoldisulfonic Acid,Nondispersive Infrared,and Saltzman Methods for the Determination of Oxides of Nitrogen in Automotive Exhaust

The Saltzman Phenoldisulfonic Acid and Nondispersive Infrared methods have been compared for the determination of oxides of nitrogen in automobile exhaust. The main purpose of this investigation was to determine whether the Nondispersive Infrared method could be used as a possible replacement for the Saltzman method. Results show that the Nondispersive Infrared analyzer can be used to measure NO_x in exhaust gases with advantages over both the Saltzman and Phenoldisulfonic Acid methods. These advantages include simplicity, speed, less complicated analytical technique, and the fact that it is better adapted to be carried out by technicians at the test site.     

Comparison of palladium and platinum in environmental matrices: Palladium pollution by automobile emissions?

A new type of automobile catalyst based on an active Pd/Rh-layer is presently being introduced into the European market. Accordingly, in order to establish baseline information, this work attempts to assess the magnitude of Pd emissions by automobile catalysts to date. Thus, a survey is presented on Pd and Pt levels detected in polluted environmental matrices (grass, soil, dust, sludges) as available from the literature. Additionally, Pd data measured by selective preconcentration/GF-AAS-detection in polluted grass, in a time series of sewage sludge ashes back to 1972, in dust, as well as in urban rain are presented. Since the data basis from the literature is partly inconsistent, the possible impact of different analytical attempts on the data is discussed. The relationship between Pt and Pd concentration from most of the results is between 5 and 10 (Pt/Pd). However, relations down to 0.04 are also reported, thus implying anthropogenic Pd input from additional sources.     

Assessment of soil lead exposure in children in Shenyang, China

Soil lead pollution is serious in Shenyang, China. The paper brings together the soil work, the bioaccessibility, and the blood lead data to assess the soil lead exposure in children in Shenyang, China. Approximately 15.25% of the samples were above China Environment Protection Agency guideline concentration for soil Pb to protect human from health risk (350 mgkg(-1)). Pb concentrations varied among use scenarios. The main lead contamination sources are industry emission and automobile exhaust. Bioaccessibility also varied among use scenarios. Children, who ingested soil from industrial area, public parks, kindergarten playground, and commercial area, are more susceptible to soil lead toxicity. The industrial area soil samples presented higher bioaccessibility compared to the other use scenario soil samples contaminated by automobile exhaust. The result also suggested a most significant linear relationship between the level of Pb contamination and the amount of Pb mobilized from soil into ingestion juice. Soil pH seemed to have insignificant influence on bioaccessibility in the present study. Bioaccessibility was mainly controlled by other factors that are not investigated in this study. A linear relationship between children blood lead and soil intestinal bioaccessibility was present in the study. Children who are 4-5 years old are more likely to demonstrate the significant relationship between soil lead bioaccessibility and blood lead as their behaviors place them at greatest risk of soil lead toxicity, and their blood lead levels are more likely to represent recent exposure.     

A review of the occurrence, analyses, toxicity, and biodegradation of naphthenic acids

Naphthenic acids occur naturally in crude oils and in oil sands bitumens. They are toxic components in refinery wastewaters and in oil sands extraction waters. In addition, there are many industrial uses for naphthenic acids, so there is a potential for their release to the environment from a variety of activities. Studies have shown that naphthenic acids are susceptible to biodegradation, which decreases their concentration and reduces toxicity. This is a complex group of carboxylic acids with the general formula CnH(2n+Z)O2, where n indicates the carbon number and Z specifies the hydrogen deficiency resulting from ring formation. Measuring the concentrations of naphthenic acids in environmental samples and determining the chemical composition of a naphthenic acids mixture are huge analytical challenges. However, new analytical methods are being applied to these problems and progress is being made to better understand this mixture of chemically similar compounds. This paper reviews a variety of analytical methods and their application to assessing biodegradation of naphthenic acids.     

Sorption of copper, zinc and lead on soil mineral phases

Soil mineral phases play a significant role in controlling heavy metal mobility in soils. The effective study of their relation needs the integrated use of several analytical methods. In this study, analytical electron microscopy analyses were combined with sequential chemical extractions on soils spiked with Cu, Zn and Pb. Our aims were to study the metal sorption capacity of soil mineral phases and the effect of presence of iron oxide and carbonate on this property of soil minerals. Copper and Pb were found to be characterized by higher and stronger sorption on the studied samples than Zn. Only the former two metals showed significant differences in their immobilized metal amounts on the studied samples and soil mineral particles. Highest metal amounts were sorbed on the swelling clay mineral particles (smectites and vermiculites), but iron-oxide phases may also have similar lead sorption capacity. Alkaline conditions due to the carbonate content of soils resulted both in increased sorption on the mineral particles for Cu and in enhanced role of precipitation for all the studied metals. On the other hand, the intimate association of phyllosilicates and iron resulted in significant increase in metal sorption capacity of the given particle. The results of sequential extractions could be successfully completed by the analytical electron microscopy analyses for studying the sorption capacity of discrete mineral particles. Their integrated use helps us in better understanding the heavy metal-mineral interactions in soils.     

Solid-state UV–MALDI–MS assay of transition metal dithiocarbamate fungicides

The determination of transition metal containing dithiocarbamate fungicides represents a challenging aspect of analytical object. They have a low stability, low solubility and stabilize versatile coordination monomers, dimers, disulfides and/or S-oxidized derivatives. Their diverse biological activities and agricultural implementation encompass plant prevention and crop protection against a variety of plants containing fungi and diseases of 400 pathogens and 70 cultures. Nonetheless, those dithiocarbamates (DTCs) are banned for agricultural use in Europe or have expiration at years 2016–2017 because of their highly toxic degradation products and/or metabolites, in particular ethylene thiourea; they found large-scale implementations in materials research and medicine. Despite the broad interdisciplinary of DTC application, due to the above reasons, they have received little attention in the rapidly growing field of analytical chemistry, and in particular, the analytical mass spectrometry. Therefore, the study reported on qualitative, quantitative and structural analysis of ten DTCs (1–10), using the matrix assisted laser desorption/ionization (UV–MALDI)–Orbitrap–mass spectrometry (MS) contributed considerably to the implementation of the method for environmental and foodstuffs monitoring. Its ultrahigh resolving power and capacity for direct solid-state analysis, at limited number of sample pretreatment steps, at concentration levels of analytes of up to femtogram per gram resulted to achievement of a highly precise analytical information for these non-trivial objects. The presented fully validated method and technique is based on the successful ionization of DTCs embedded in three novel organic salts (M₁–M₃). In this regard, the reported MS and the single-crystal X-ray diffraction data as well as the quantum chemical one are able to correlate the molecular structures in condense and in the gas phase. Despite the novelty of the fundamental methodological character of the research reported, the promising metrology contributed to the applied aspect of the UV–MALDI–MS as a robust analytical method for environmental and foodstuffs monitoring, which is tested on two commercially available crop protecting products such as Mancozeb® and Antracol®, respectively.     

Loading estimates of lead, copper, cadmium, and zinc in urban runoff from specific sources

Urban stormwater runoff is being recognized as a substantial source of pollutants to receiving waters. A number of investigators have found significant levels of metals in runoff from urban areas, especially in highway runoff. As an initiatory study, this work estimates lead, copper, cadmium, and zinc loadings from various sources in a developed area utilizing information available in the literature, in conjunction with controlled experimental and sampling investigations. Specific sources examined include building siding and roofs; automobile brakes, tires, and oil leakage; and wet and dry atmospheric deposition. Important sources identified are building siding for all four metals, vehicle brake emissions for copper and tire wear for zinc. Atmospheric deposition is an important source for cadmium, copper, and lead. Loadings and source distributions depend on building and automobile density assumptions and the type of materials present in the area examined. Identified important sources are targeted for future comprehensive mechanistic studies. Improved information on the metal release and distributions from the specific sources, along with detailed characterization of watershed areas will allow refinements in the predictions.     

基于GIS城市机动车尾气扩散迁移研究

中国城市大气污染日趋严重，汽车尾气污染所占比重越来越大。交通、道路、管制及气候条件等是影响城市机动车尾气排放的主要因素。本文根据机动车尾气研究的实际，研究了专题MGIS数据库结构， 并以广州为例，建立了基于GIS的城市机动车尾气扩散迁移预报系统，在此基础上实现了机动车尾气污染状况的可视化。     

Occurrence, behavior and effects of nanoparticles in the environment

The increasing use of engineered nanoparticles (NP) in industrial and household applications will very likely lead to the release of such materials into the environment. Assessing the risks of these NP in the environment requires an understanding of their mobility, reactivity, ecotoxicity and persistency. This review presents an overview of the classes of NP relevant to the environment and summarizes their formation, emission, occurrence and fate in the environment. The engineered NP are thereby compared to natural products such as soot and organic colloids. To date only few quantitative analytical techniques for measuring NP in natural systems are available, which results in a serious lack of information about their occurrence in the environment. Results from ecotoxicological studies show that certain NP have effects on organisms under environmental conditions, though mostly at elevated concentrations. The next step towards an assessment of the risks of NP in the environment should therefore be to estimate the exposure to the different NP. It is also important to notice that most NP in technical applications are functionalized and therefore studies using pristine NP may not be relevant for assessing the behavior of the NP actually used.     

Nanoanalytics: history,concepts, and specificities

Environmental Science and Pollution Research - This article deals with analytical chemistry devoted to nano-objects. A short review presents nano-objects, their singularity in relation to their...     

New trends in the analytical determination of emerging contaminants and their transformation products in environmental waters

Since the so-called emerging contaminants were established as a new group of pollutants of environmental concern, a great effort has been devoted to the knowledge of their distribution, fate and effects in the environment. After more than 20 years of work, a significant improvement in knowledge about these contaminants has been achieved, but there is still a large gap of information on the growing number of new potential contaminants that are appearing and especially of their unpredictable transformation products. Although the environmental problem arising from emerging contaminants must be addressed from an interdisciplinary point of view, it is obvious that analytical chemistry plays an important role as the first step of the study, as it allows establishing the presence of chemicals in the environment, estimate their concentration levels, identify sources and determine their degradation pathways. These tasks involve serious difficulties requiring different analytical solutions adjusted to purpose. Thus, the complexity of the matrices requires highly selective analytical methods; the large number and variety of compounds potentially present in the samples demands the application of wide scope methods; the low concentrations at which these contaminants are present in the samples require a high detection sensitivity, and high demands on the confirmation and high structural information are needed for the characterisation of unknowns. New developments on analytical instrumentation have been applied to solve these difficulties. Furthermore and not less important has been the development of new specific software packages intended for data acquisition and, in particular, for post-run analysis. Thus, the use of sophisticated software tools has allowed successful screening analysis, determining several hundreds of analytes, and assisted in the structural elucidation of unknown compounds in a timely manner.     

Impact of humic substances on the aqueous solubility, uptake and bioaccumulation of platinum, palladium and rhodium in exposure studies with Dreissena polymorpha

Zebra mussels (Dreissena polymorpha) were exposed to different types of water containing PGE salts (PtCl4, PdSO4, RhCl3) to investigate the influence of humic substances on the aqueous solubility, uptake and bioaccumulation of noble metals. The results showed a time dependent decrease of the aqueous PGE concentrations in tank water for all groups. This could mainly be related to non-biological processes. The aqueous solubility of Pd and Rh was higher in humic water compared with non-chlorinated tap water, whereas Pt showed opposing results. Highest metal uptake rates and highest bioaccumulation plateaus were found for Pd, followed by Pt and Rh. Pd uptake and bioaccumulation was significantly hampered by humic substances, whose presence appear to increase Pt uptake and bioaccumulation. No clear trend emerged for Rh. Differences in effects of humic matter among the PGE may be explained by formation of metal complexes with different fractions of humic substances.     

Heavy metals in agricultural soils of the Pearl River Delta,South China

There is a growing public concern over the potential accumulation of heavy metals in agricultural soils in China owing to rapid urban and industrial development and increasing reliance on agrochemicals in the last several decades. Excessive accumulation of heavy metals in agricultural soils may not only result in environmental contamination, but elevated heavy metal uptake by crops may also affect food quality and safety. The present study is aimed at studying heavy metal concentrations of crop, paddy and natural soils in the Pearl River Delta, one of the most developed regions in China. In addition, some selected soil samples were analyzed for chemical partitioning of Co, Cu, Pb and Zn. The Pb isotopic composition of the extracted solutions was also determined. The analytical results indicated that the crop, paddy and natural soils in many sampling sites were enriched with Cd and Pb. Furthermore, heavy metal enrichment was most significant in the crop soils, which might be attributed to the use of agrochemicals. Flooding of the paddy soils and subsequent dissolution of Mn oxides may cause the loss of Cd and Co through leaching and percolation, resulting in low Cd and Co concentrations of the paddy soils. The chemical partitioning patterns of Pb, Zn and Cu indicated that Pb was largely associated with the Fe-Mn oxide and residual fractions, while Zn was predominantly found in the residual phase. A significant percent fraction of Cu was bound in the organic/sulphide and residual phases. Based on the 206Pb/207Pb ratios of the five fractions, it was evident that some of the soils were enriched with anthropogenic Pb, such as industrial and automobile Pb. The strong associations between anthropogenic Pb and the Fe-Mn oxide and organic/sulphide phases suggested that anthropogenic Pb was relatively stable after deposition in soils.     

Sampling,occurrence and evaluation of PCDDs and PCDFs from incinerated solid urban waste

The sampling procedure of solid and gaseous pollutants, contained in flue gas emitted into the atmosphere by solid waste incinerating furnaces were investigated. Because of their extraordinary toxicological properties, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are taken into particular consideration. The analytical work is based on the use of high-resolution gas chromatography in combination with low-resolution mass spectrometry. Details of the extensive sample clean-up will follow the GC-MS separation and identification of the isomers detected for each group of PCDDs and PCDFs. Quantitative data of these pollutants distribution levels deriving from different investigated incinerators are also reported.     

A case study of contaminants on military ranges: Camp Edwards, Massachusetts, USA

An extensive investigation at the Camp Edwards, Massachusetts Military Reservation (MMR) demonstrates that assessment of groundwater and soil contamination at military ranges can be limited primarily to explosive-related compounds such as RDX, HMX, perchlorate, TNT and their transformation products. A modified analytical method is recommended to expand the list of explosives and to improve the detection limits. Analyses of metals, VOCs, SVOCs, and TICs are unnecessary. Soil samples may require the analyses of PAHs and PCNs for burn areas. Camp Edwards, as one of the few military ranges that have been exhaustively investigated for contaminants, is an ideal point of departure for evaluating other ranges. The permeable site soils promote leaching of contaminants and inhibit biotic and abiotic transformations. Moreover, the site has experienced an unusual extent of activities in its more than ninety years of active use. The recommendations in this report are based on data obtained for more than 200 analytes from more than 15,000 environmental samples.     

First report on the uptake of automobile catalyst emitted palladium by European eels (Anguilla anguilla) following experimental exposure to road dust.

Following the introduction of automobile catalysts in the middle of the 1980s in Germany there is an increasing emission of the platinum-group-metals platinum, palladium (Pd) and rhodium. Still, it remains unclear if these metals are bioavailable for aquatic animals and to which extent they become accumulated by the aquatic biosphere. Because of analytical problems in detecting Pd in small biological samples the present investigation concentrates on the bioavailability of this metal. To answer the question of a Pd uptake by aquatic organisms experimental studies were conducted with European eels maintained in water containing road dust at a concentration of 10 kg/100 l. Following an exposure period of four weeks, samples of liver and kidney were analysed by total-reflection X-ray fluorescence analysis after co-precipitation of Pd with mercury. These experiments revealed an uptake of traffic related Pd by European eels which showed a mean liver Pd concentration of 0.18 +/- 0.05 ng/g (wet wt.), whereas the Pd concentration in the kidney ranged below the detection limit. Thus, in this study we can demonstrate for the first time that automobile catalyst emitted Pd is bioavailable for aquatic animals.     

Ambient Air Quality and Automotive Emission Control

This paper is concerned with uncertainties involved in projecting ambient air quality. Ambient air quality was projected by assuming a linear dependence on estimated future emissions. Future automotive emissions were estimated by a method recommended by EPA. Projections were made for the locations reported to have the highest ambient air concentrations of each pollutant; Chicago for carbon monoxide and the California South Coast Air Basin for hydrocarbon and oxidant. The sensitivity of the projections to several input parameters was determined.

The uncertainty in projection of air quality due to the use of a maximum, once-per-year concentration is large. For example, the reduction in total CO emissions in Chicago in 1975, necessary to meet the air quality standard, was as high as 68% or as low as 26%, depending on whether the historic high, 8 hr average concentration of 44 ppm or the 1970 maximum of 21 ppm was used. The effects of uncertainties in growth rates and fraction of emissions attributed to the automobile were also sizeable. Differences in automotive growth rate had a large near-term effect on projected concentrations, while differences in nonautomotive growth rate or fraction of emissions attributed to the automobile had a large long-term effect. The effect of 1975 interim automotive emission standards on projected air quality was negligible when compared with projected air quality based on the previous Federal automotive emission standards for 1975.     

Occurrence of polybrominated diphenylethers, polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls in coastal sediments from Spain

Fifteen sediment samples were analysed in order to determine their content of polybrominated diphenylethers (PBDEs), polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs). Samples were collected from several hot spots on the Spanish coast, such as the harbours of Almeria and Tarragona, and the mouths of the Besos and Llobregat rivers in Barcelona. A generic analytical procedure based on Soxhlet extraction followed by an automated cleanup system and gas chromatography-ion trap-mass spectrometry was employed for determining the toxic congeners of PCDDs and PCDFs, as well as dioxin-like PCBs. As regards PBDE determinations, a rapid method based on the use of selective pressurized liquid extraction followed by gas chromatography-negative ion chemical ionization-mass spectrometry was applied. Total toxicity equivalent (WHO-TEQ) values were calculated using the toxicity equivalent factors proposed by WHO for dioxin-like PCBs, PCDDs and PCDFs. WHO-TEQ values ranged from 0.3 to 75 pg/g dry weight (dw), with PCB contribution on the toxicity of the samples between 1 and 84%. Total PBDE levels ranged from 2.7 to 134 ng/g dw, with BDE-209 contribution on the total PBDE contamination between 50 and 99%.     

Trace elements accumulation and their variations with growth, sex and habitat: effects on Formosan squirrel (Callosciurus erythraeus)

Formosan squirrels are considered a useful bio-indicator because their habitat exists within that of humans. Therefore, concentrations of 19 trace elements were determined in tissues of this species for assessment of environmental pollution in urban Kamakura and rural Izuohshima. Results of analyses revealed high Cu concentrations in the livers of Formosan squirrels. Moreover, concentrations of some trace elements from automobile exhausts-V, Zn, Cu and As-in the specimens from Kamakura were higher than those from Izuohshima. These results reflect the presence of pollution caused by human activities in Kamakura.