Feasibility of coupling a thermal/optical carbon analyzer to a quadrupole mass spectrometer for enhanced PM2.5 speciation

A thermal/optical carbon analyzer (TOA), normally used for quantification of organic carbon (OC) and elemental carbon (EC) in PM_2.5 (fine particulate matter) speciation networks, was adapted to direct thermally evolved gases to an electron impact quadrupole mass spectrometer (QMS), creating a TOA-QMS. This approach produces spectra similar to those obtained by the Aerodyne aerosol mass spectrometer (AMS), but the ratios of the mass to charge (m/z) signals differ and must be remeasured using laboratory-generated standards. Linear relationships are found between TOA-QMS signals and ammonium (NH₄⁺), nitrate (NO₃^?), and sulfate (SO₄^2-) standards. For ambient samples, however, positive deviations are found for SO₄^2-, compensated by negative deviations for NO₃^?, at higher concentrations. This indicates the utility of mixed-compound standards for calibration or separate calibration curves for low and high ion concentrations. The sum of the QMS signals across all m/z after removal of the NH₄⁺, NO₃^?, and SO₄^2- signals was highly correlated with the carbon content of oxalic acid (C?H?O?) standards. For ambient samples, the OC derived from the TOA-QMS method was the same as the OC derived from the standard IMPROVE_A TOA method. This method has the potential to reduce complexity and costs for speciation networks, especially for highly polluted urban areas such as those in Asia and Africa.

Implications: Ammonium, nitrate, and sulfate can be quantified by the same thermal evolution analysis applied to organic and elemental carbon. This holds the potential to replace multiple parallel filter samples and separate laboratory analyses with a single filter and a single analysis to account for a large portion of the PM_2.5 mass concentration.     

Trace metal (Cd,Cu, Pb,Zn) fractionation in urban-industrial soils of Ust-Kamenogorsk (Oskemen), Kazakhstan—implications for the assessment of environmental quality

Ust-Kamenogorsk is one of the largest cities and industrial centers in Kazakhstan. Non-ferrous metallurgy (Zn–Pb smelter) has acted as a predominating industrial branch in the city since late 1940s. The industrial plants are situated directly adjacent to the residential area of the city which creates grievous ecotoxicological hazard. In the present paper, we aimed at assessing the trace metal pollution of top soils in Ust-Kamenogorsk and its potential threats to the local population. The top soils were sampled at 10 sites throughout the city center. We determined the physical and chemical properties of soils as well as the contents of Cd, Cu, Pb, and Zn. In addition, the soil samples were subjected to a five-step sequential extraction to ascertain the fractionation of trace metals. On this basis, we calculated the geoaccumulation index (I_geo) and pollution load index (PLI) and assessed bioavailability of the elements. From our data, it emerged that the soils displayed a strong polymetallic pollution. PLI was as high as 33.4. Throughout the city, the trace metal contents exceeded the geochemical background and allowable values for residential, recreational, and institutional areas. The I_geo obtained were 3.7–6.5 for Cd, 1.5–4.7 for Cu, 2.8–5.7 for Pb, and 2.6–4.6 for Zn. The soils in Ust-Kamenogorsk displayed extremely high contamination with Cd, moderate to strong contamination with Pb and Zn, and low to moderate contamination with Cu. Cd and Pb were found to be the most bioavailable elements. The mobility of trace metals in the soils changed in the order Cd > Pb > Zn > Cu.     

Development of an efficient and sensitive analytical method for the determination of copper at trace levels by slotted quartz tube atomic absorption spectrometry after vortex-assisted dispersive liquid-liquid microextraction in biota and water samples using a novel ligand

This study describes the determination of trace levels of copper by slotted quartz tube atomic absorption spectrometry after dispersive liquid-liquid microextraction. A ligand synthesized from the reaction of salicylaldehyde and 1-naphthylamine was used to form coordinate copper complex prior to extraction. All parameters that influence the output of complex formation, extraction, and instrumental measurement were optimized to enhance the absorbance signal of copper. Under the optimum conditions, about 104-fold enhancement in sensitivity was recorded over the conventional flame atomic absorption spectrometer, corresponding to a 0.51 ng/mL detection limit. The percent relative standard deviation calculated for the lowest concentration (4.8%) indicated high precision for the experimental procedure. Accuracy and applicability of the optimum method were determined by performing spiked recovery tests on urine, lake water, and mineral water samples. Satisfactory recovery results were obtained between 82.2 and 106.3% at four different concentrations. Matrix matching method was also performed to increase the accuracy of quantification, and the percent recovery calculated for 175 ng/mL was 105.14%.     

Quantification of forest fragmentation in pre- and post-establishment periods,inside and around Apuseni Natural Park,Romania

Protected areas (PAs) represent real cornerstones in the conservation of biodiversity and natural habitats. Their protection must be a priority today for each society. The enhanced socio-economic requirements increase the pressure upon protected areas, and the effect can result in a reduction of biodiversity. The aim of this study is to quantify forest fragmentation in the pre- (1986–2002) and post-establishment (2002–2016) periods, inside and around (buffer 1, buffer 2 and buffer 3) Apuseni Natural Park (ANP), Romania, using a series of classified Landsat satellite images and six landscape metrics. The results show that forest fragmentation occurred both in the pre- and post-establishment periods, inside and around ANP. Inside the park, the deforestation rate increased four times, from 0.03% year^?1 in the pre-establishment period to 0.14% year^?1 in the post-establishment period. Around the park, the deforestation rate decreased from 0.31% year^?1 in the pre-establishment period (buffer 1) to 0.10% year^?1 in the post-establishment period (buffer 1). Forest fragmentation resulted in an increase in the patch density and edge density, and a decrease in the total core area and mean patch size leading to isolation of patches and fragmentation of landscape, especially in ANP in the post-establishment period. Several measures can be taken in order to stop forest fragmentation inside and around ANP, including the education of buffer-zone communities, reforestation, enforcement of park regulations, and forest legislation.     

The distribution and enrichment characteristics of copper in soil and <Emphasis Type="Italic">Phragmites australis</Emphasis> of Liao River estuary wetland

The aims of the present investigation were to reveal the distribution and enrichment characteristics of copper in soil and Phragmites australis of Liao River estuary wetland. The concentrations of copper in root, stem, leaf, and ear of Phragmites australis as well as in soil were determined to study the absorption capacity of copper by wild Phragmites australis of Liao River estuary wetland. The study was carried out at test pool of the Shenyang Agricultural University, and the experimental materials (soil, irrigating water and Phragmites australis) were derived from Liao River estuary wetland. The concentrations of copper in soil and Phragmites australis were 16.4441 to 49.0209 mg/kg and 0.8621 to 89.5524 mg/kg, respectively. The results indicated that the enrichment coefficients of copper in different tissues of Phragmites australis changed with the growth of Phragmites australis. The results revealed that the enrichment coefficients of copper in the whole Phragmites australis were greater than 1 at each growing stage of the Phragmites australis. The results also showed that the transfer coefficients of Phragmites australis to copper changed with the growth of Phragmites australis. The results revealed that the Phragmites australis had a good removal effect on copper from soil and had some characteristics of copper hyperaccumulator.     

A multivariate examination of ‘artificial mussels’ in conjunction with spot water tests in freshwater ecosystems

Metal pollution in aquatic systems is considered a serious environmental issue globally due to their ability to accumulate in aquatic environments. Wetlands are vulnerable to this pollution as they are known to trap toxins, removing them from the water. Artificial mussel technology, originally developed for marine environments, was applied to this freshwater system and spot water samples were collected. The Nyl River floodplain (Ramsar classified) is one of the largest and most ecologically significant wetlands in South Africa. The aims of this study were to determine metal contamination along the Nyl River system by means of artificial mussels (AM) and water ICP-MS analysis and to determine whether the use of AMs in conjunction with spot water testing could give more insight into the pollution in freshwater wetlands. The concentrations of Al, Cd, Cr, Co, Cu, Fe, Mn, Ni, Pb and Zn were determined at seven sites. It was determined that the levels accumulated by the AMs differed in spatial and temporal trends when compared to spot water samples. It was determined that there were high levels of some metals found in the spot water tests that were not corroborated by the AMs results, which could indicate isolated pollution events. The use of AMs in conjunction with spot water testing was determined to be beneficial in gaining deeper insight into water metal conditions in dynamic freshwater systems.     

A synoptic survey of select wastewater-tracer compounds and the pesticide imidacloprid in Florida’s ambient freshwaters

Current wastewater treatment technologies do not remove many unregulated hydrophilic compounds, and there is growing interest that low levels of these compounds, referred to as emerging contaminants, may impact human health and the environment. A probabilistic-designed monitoring network was employed to infer the extent of Florida’s ambient freshwaters containing the wastewater (Includes reuse water, septic systems leachate, and wastewater treatment effluent.) indicators sucralose, acetaminophen, carbamazepine, and primidone and those containing the widely used pesticide imidacloprid. Extent estimates with 95% confidence bounds are provided for canals, rivers, streams, small and large lakes, and unconfined aquifers containing ultra-trace concentrations of these compounds as based on analyses of 2015 sample surveys utilizing 528 sites. Sucralose is estimated to occur in greater than 50% of the canal, river, stream, and large lake resource extents. The pharmaceuticals acetaminophen, carbamazepine, and primidone are most prevalent in rivers, with approximately 30% of river kilometers estimated to contain at least one of these compounds. Imidacloprid is estimated to occur in 50% or greater of the canal and river resource extents, and it is the only compound found to exceed published toxicity or environmental effects standards. Geospatial analyses show sucralose detection frequencies within Florida’s drainage basins to be significantly related to the percentage of urban land use (R²?=?0.36, p?<?0.001), and imidacloprid detection frequencies to be significantly related to the percentage of urban and agricultural land use (R²?=?0.47, p?<?0.001). The extent of the presence of these compounds highlights the need for additional emerging contaminant studies especially those examining effects on aquatic biota.     

Carbon and nitrogen mineralization in Vertisol as mediated by type and placement method of residue

Selection of appropriate residue application method is essential for better use of biomass for soil and environmental health improvement. A laboratory incubation experiment was conducted for 75 days to investigate C and N mineralization of residues of soybean (Glycine max L.), chickpea (Cicer arietinum L.), maize (Zea mays L.), and wheat (Triticum aestivum L.) placed on the soil surface and incorporated into the soil. The residue of soybean and chickpea had a greater decomposition rate than that of maize and wheat, despite of their placements. Higher rate of decomposition of the residue of soybean and chickpea was recorded when it was kept on the soil surface while soil incorporation of residue of wheat and maize resulted in faster decomposition. Therefore, these findings could be used as guidelines for management of crop residue application in farmland to improve soil and environmental quality.     

Saharan dust particles in snow samples of Alps and Apennines during an exceptional event of transboundary air pollution

Southern European countries are often affected in summer by transboundary air pollution from Saharan dust. However, very few studies deal with Saharan dust pollution at high altitudes in winter. In Italy, the exceptional event occurred on February 19, 2014, colored in red the entire mountain range (Alps and Apennines) and allowed to characterize the particulate matter deposited on snow from a morphological and chemical point of view. Snow samples were collected after this event in four areas in the Alps and one in the Apennines. The particulate matter of the melted snow samples was analyzed by scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDS) and by inductively coupled plasma mass spectrometry (ICP-MS). These analyses confirmed the presence of Saharan dust particle components in all areas with similar percentages, supported also by the positive correlations between Mg-Ca, Al-Ca, Al-Mg, and Al-K in all samples.