Determination of atmospheric nitrogen input to Lake Greenwood,South Carolina--I. PM measurements

The Reedy River branch of Lake Greenwood, SC, has repeatedly experienced summertime algal blooms, upsetting the natural system. This lake's shallow depth makes It susceptible to atmospheric influence. A series of experiments were carried out in order to investigate the effect of atmospheric nitrogen deposition into the lake. Nitrogen was examined because of the insignificant phosphorus dry atmospheric flux and the unique nutrient demands of the dominant algae (Pithophora oedogonia) contributing to the blooms. In this paper, results are presented, of the experimental measurement of coarse and fine atmospheric concentrations of atmospheric particulate nitrogen adjacent to and in the watershed of the Reedy River (downtown Greenville) and Lake Greenwood. Experiments were carried out during four 24-hr periods in January 2001 and again during four 24-hr periods in March 2001. Results are presented here for atmospheric particulate nitrogen as well as other constituents of the airborne aerosol. Mass concentrations of PM2.5 averaged 14.0 and 21 microg/m3 for Lake Greenwood and downtown Greenville, respectively. Mass concentrations of total suspended particulates (TSP) averaged 22.6 and 38.5 microg/m3 for Lake Greenwood and downtown Greenville, respectively. This ambient aerosol concentration was apportioned to its chemical constituents, and the greatest contributors to PM2.5 mass were organics (45 and 42% for downtown Greenville and the lake, respectively) and sulfate (14.1 and 19.7% for downtown Greenville and the lake, respectively). The information gathered here, despite its episodic nature, is important not only in determining atmospheric nitrogen but also in documenting the composition of aerosol in South Carolina, which so far has not been studied. In a companion paper, results for gaseous pollutants as well as thermodynamic modeling of the aerosol and nitrogen flux determinations are presented.     

Determination of atmospheric nitrogen input to Lake Greenwood, South Carolina: part 2--Gaseous measurements and modeling

The Reedy River branch of Lake Greenwood, SC, has repeatedly experienced summertime algal blooms, upsetting the natural system. A series of experiments were carried out to investigate atmospheric nitrogen (N) input into the lake. N was examined because of the insignificant phosphorus dry atmospheric flux and the unique nutrient demands of the dominant algae (Pithophora oedogonia) contributing to the blooms. Episodic atmospheric measurements during January and March 2001 have shown that the dry N flux onto the lake ranged from 0.9 to 17.4 kg N/ha-yr, and on average is caused by nitric acid (HNO3; 31%), followed by nitrogen dioxide (NO2; 23%), fine ammonium (NH4+; 20%), coarse nitrate (NO3-; 16%), fine NO3 (5%), and coarse NH4+ (5%). Similar measurements in Greenville, SC (the upper watershed of the Reedy River), showed that the dry N deposition flux there ranged from 1.4 to 9.7 kg N/ha-yr and was mostly caused by gaseous deposition (40% NO2 and 40% HNO3). The magnitude of this dry N deposition flux is comparable to wet N flux as well as other point sources in the area. Thermodynamic modeling showed low concentrations of ammonia, relative to the particulate NH4+ concentrations.     

Veränderungen des NO/NO2-Verhältnisses in Nordrhein-Westfalen (1984–2004) und mögliche Ursachen

Objective and Background

The nitrogen oxides NO and NO₂ and, in particular, their ratio (NO/NO₂), play important roles in the radical-system of the atmospheric boundary layer. There were various indications upon a dropping NO/NO₂-ratio in citiex over the last years, however, no proof has been given yet Especially in densely populated areas such as the federal state of North Rhine-Westphalia (NRW), such a change can have significant influences upon various atmospheric reactions. The objective of this investigation was to prove the existence of a systematic change of the NO/NO₂-ratio, to describe the development of NO_x over the past 2 decades at different locations and to determine the causes for this development.

Methods

To detect changes of the NO/NO₂-ratio we processed the data of 11 continuously operating air quality stations of the State Environment Agency (LUA NRW) with time series reaching back up to 20 years. We investigated rural stations, stations in the urban background and heavily traffic influenced locations. It was possible to calculate and assess the NO/NO₂-ratio under consideration of the fast reaction of ozone with NO. There were clear indications towards existing trends and they could be determined as statistically significant using the nonparametric Mann-Kendall Test. The analysis of possible causes for the change of the NO/NO₂-ratio focused upon the change of the global radiation, the change of the patterns of the atmosphetic circulation, and the frequency of cyclones and anticyclones meteorological conditions in Central Europe, the introduction of automotive catalytic converters, and the development of the atmospheric oxidation-capacity.

Results and conclusions

The results are indicating a decline of the ratio at traffic-influenced stations with a statistical significance over 95%. The negative trend can also be detected at most urban background stations. It was problematic to perform the trend-analysis of the rural background station in the Egge-Mountains because of the fragmentary character of the dataset. Regional differences in the development of the NO/NO₂-ratio indicate towards various causes. Crucial for the situation at the rural areas are the changed trajectories of cyclones and anticyclones as well as the decline of the atmospheric oxidation-capacity, while the traffic plays another important role at urban stations. The negative trend at the traffic-stations was intensified by the introduction of catalytic converters, which lead to a reduction in emissions of NO_x

Recommendations and prospects

The significance of the NO/NO₂-ratio for the oxidation capacity of the atmosphere shows the necessity to further monitor this development. Previous investigations detected a decline in total NO_x without examining the relative development of the two nitrogen oxides towards each other. Gaining insight into the local differences of this ratio helps to allocate sources and to develop understanding of the atmospheric processes.     

The assessment of the energetic compound 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-Hexaazaisowurtzitane (CL-20) degradability in soil

CL-20 is a relatively new energetic compound with applications in explosive and propellant formulations. Currently, information about the fate of CL-20 in ecological systems is scarce. The aim of this study is to evaluate the biodegradability of CL-20 in soil environments. Four soils were used where initial CL-20 concentrations (above water solubility) ranged from 125 to 1500 mg of CL-20 per kg dry soil (corresponding to the concentrations derived from unexploded ordnance, low order detonation, or manufacturing spills). CL-20 appears to be biodegradable in soil under anaerobic conditions, and additions of organic substrates can substantially accelerate this process. However, CL-20 is not degraded in soil under aerobic conditions kept in the dark at temperatures up to 30 degrees C without organic amendments. Additions of starch or cellulose promote the biodegradation of CL-20 under aerobic conditions. Soil microbial community mediated biodegradation and plant uptake appears to enhance CL-20 biodegradation, the latter suggesting a possible route for CL-20 to entry in the food chain.     

Technical modeling in integrated risk assessment of chemical installations

This paper presents the technical model of an Integrated Quantitative Risk Assessment method, taking into account management as well as technical design and producing risk level measures. The basic steps of the technical model consist in developing a Master Logic Diagram (MLD) delineating the major immediate causes of Loss of Containment and associated quantitative models for assessing their frequency. Appropriate management models quantify the parameters of the technical model on the basis of the safety management system of the installation. The methodology is exemplified through its application on the risk assessment of a LPG scrubbing tower of an oil refinery. A detailed technical model simulating the response of the system to various initiating events is developed, along with a detailed model simulating the influence of the plant-specific management and organizational practices. The overall effect is quantified through the frequency of release of LPG as a result of a Loss of Containment in scrubbing towers of the refinery.     

Determination of dithiocarbamate fungicide propineb and its main metabolite propylenethiourea in airborne samples

A simple, rapid and sensitive GC–MS method for the determination of dithiocarbamate fungicide propineb [polymeric zinc propylenebis (dithiocarbamate)] and an improved HPLC procedure for the simultaneous determination of its main metabolite, propylenethiourea, and ethylenethiourea, the main metabolite of all ethylenedithiocarbamates, in airborne samples are described. The method for the analysis of propineb involves the evolution of carbon disulfide (CS₂), under acidic conditions in the presence of stannous chloride, extraction of the generated CS₂ into a layer of isooctane which is then analyzed for CS₂ content by GC–MS in SIM mode. Under the optimum conditions, the retention time of CS₂ was 1.89 min and the total time of chromatographic analysis was 5 min. Recoveries from spiking glass microfibre filters (GF/A) and silica gel filters were 86 ± 7 (n = 9) and 89 ± 4 (n = 9), respectively. The limit of detection is 0.7 ng per filter, which is equivalent to about 0.8–1.0 ng m⁻³ in air. In parallel, an HPLC method with ultraviolet detection is presented for the simultaneous analysis of the metabolites. Separation of the two metabolites was attained in less than 5 min. Recoveries from spiking GF/A and silica gel filters for ethylenethiourea were 100 ± 1 (n = 3) and 98 ± 2 (n = 3), respectively, while for propylenethiourea were 102 ± 1 (n = 3) and 98 ± 1 (n = 3), respectively. The detection limits are about 36–43 and 40–49 ng m⁻³ in air for ethylenethiourea and propylenethiourea, respectively. All the analytes spiked in the filters are proven to be stable for more than one month, at −4 °C.     

Strictly protected areas are not necessarily more effective than areas in which multiple human uses are permitted

The International Union for Conservation of Nature (IUCN) classifies protected areas into six categories, ranging from strict nature reserves to areas where multiple human uses are permitted. In the past, many researchers have questioned the effectiveness of multiple-use areas, fueling an unresolved debate regarding their conservation value. The literature so far has been inconclusive: although several studies have found that strictly protected areas are more effective, others have found the opposite, and yet others that the two types do not differ. To help resolve this debate, we reviewed the literature on protected areas and conducted our own analysis using > 19 000 terrestrial protected areas worldwide. We found that the differences between strictly protected areas and areas in which multiple human uses are permitted are often small and not statistically significant. Although the effectiveness of protected areas worldwide varies, other factors, besides their assigned IUCN category, are likely to be driving this pattern.Electronic supplementary materialThe online version of this article (10.1007/s13280-020-01426-5) contains supplementary material, which is available to authorized users.