On-line speciation of arsenical compounds in fish and mussel extracts by HPLC-ICP-MS

The separation and determination of sub-μmol/l levels of six environmentally significant As compounds was accomplished by means of high performance liquid chromatography (HPLC) combined online with inductively coupled plasma mass spectrometry (ICP-MS). The species of interest (arsenite and arsenate, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine and arsenocholine) were quantified in fish and mussel extracts after separation on a Dionex AS7 column equipped with an on-guard AG7 column using a bicarbonate buffer as the mobile phase in a gradient mode. The species thus eluted were directly forwarded to the ICP-MS detector. The detection power of the overall system allows each As form to be determined at concentrations as low a 0.0013–0.0027 μmol 1⁻¹.     

Invasion of Pinus halepensis Mill. following a wildfire in an Argentine grassland nature reserve

The Ernesto Tornquist nature reserve is a relict of native Pampas vegetation in Argentina. Alien trees were introduced to the reserve in the 1950s, mainly to "improve" the natural landscape, resulting in the arrival of a totally new life form. In 1987, a fire affected an area planted with Pinus halepensis resulting in its massive expansion. In 1999, we removed trees from 17 circular plots of 10 m diameter placed systematically within the area that was colonized after the fire. Trunks were cut 20 cm from the ground and growth rings were counted. We studied the age structure of the population in order to reconstruct the colonizing events after the fire. We found that recruitment occurred throughout this period, except in the three years after the disturbance. We suggest that this delay in recruitment might be caused by low seedling survival under water stress conditions due to low rainfall, combined with scarce vegetation cover after fire. This could have been associated with an initial reduction in propagule pressure due to the scarcity of surviving trees in the vicinity and with the fact that fire occurred after the peak of seed release, during an extremely dry summer, probably killing a great number of seeds that were already in the soil. In the following years, recruitment was probably aided by pioneer trees and later by seeds shed from established pines. Alien trees had been allowed to reach maturity due to wildfire prevention and control in the years preceding the fire and the accumulated dry matter resulted in increased fire intensity that reduced the ability of grasses to re-sprout. As a consequence, the invasion window that allowed the expansion of pines remained open for at least 12 years.     

Effects of soil moisture depletion on vegetable crop uptake of pharmaceuticals and personal care products (PPCPs)

Agricultural crops have a long history of being irrigated with recycled wastewater (RW). However, its use on vegetable crops has been of concern due to the potential prevalence of microcontaminants, such as pharmaceuticals and personal care products (PPCPs) in the latter, which represents a possible health hazard to consumers. We investigated the uptake of three PPCPs (atenolol, diclofenac, and ofloxacin), at three different concentrations in irrigation water (0.5, 5, and 25 μg L^?1) in relation to three varying volumetric soil moisture depletion levels of 14 % (?4.26 kPa), 10 % (?8.66 kPa), and 7 % (?18.37 kPa) by various vegetable crop species. Experiments were conducted in a split-split block completely randomized design. PPCPs were extracted using a developed method of accelerated solvent extraction and solid phase extraction and analyzed via liquid chromatography mass spectrometry (LCMS). Results indicate that all treated crops were capable of PPCP uptake at nanogram per gram concentrations independent of the applied soil moisture depletion levels and PPCP concentrations. Ofloxacin was the chemical with the highest uptake amounts, followed by atenolol and then diclofenac. Although the results were not statistically significant, higher concentrations of PPCPs were detected in plants maintained under higher soil moisture levels of 14 % (?4.26 kPa).     

Salinity variations in the water resources fed by the Etnean volcanic aquifers (Sicily, Italy): natural vs. anthropogenic causes

In this paper, in an attempt to reveal possible changes connected to natural or anthropogenic causes, the main results of hydrogeochemical monitoring carried out at Mount Etna are evaluated. We report on the salinity contents of the groundwaters that flow in fractured volcanics, which make up the flanks of the volcano. These waters, analyzed for major ion chemistry, were sampled regularly from 1994 to 2004. Basing on nonparametric Sen??s slope estimator, time series of groundwater composition reveal that the salinity of most of the Etnean aquifers increased by 0.5% to 3.5% each year during this period. This change in the water chemistry is clearly referable to the overexploitation of the aquifers. This increasing trend needs to be inverted urgently; otherwise, it will cause a shortage of water in the near future, because the maximum admissible concentration of salinity for drinking water will be exceeded.     

Removal of heavy metal ions from wastewaters using dendrimer-functionalized multi-walled carbon nanotubes

Dendrimer-functionalized multi-walled carbon nanotubes (MWCNT) for heavy metal ion removal from wastewaters were developed. Triazole dendrimers (TD) were built directly onto the carbon nanotube surface by successive click chemistry reactions affording the zero- and first-generation dendrimer-functionalized MWCNT (MWCNT-TD1 and MWCNT-TD2). The Moedritzer-Irani reaction carried out on the amino groups present on the MWCNT-TD2 sample gave the corresponding α-aminophosphonate nanosystem MWCNT-TD2P. Both MWCNT-TD2 and MWCNT-TD2P nanosystems have been characterized by physical, chemical, and morphological analyses. Their chelating abilities towards the toxic metal ions Pb²⁺, Hg²⁺, and Ni²⁺ and the harmless Ca²⁺ ion have been experimentally evaluated in the two different sets of experiments and at the salt concentrations of 1 mg/mL or 1 μg/mL by inductively coupled plasma mass spectrometry (ICP-MS). The results of these studies pointed out the interesting chelating behavior for the phosphonated nanosystem towards the Hg²⁺ ion. The complexation mode of the best chelating system MWCNT-TD2P with mercury was investigated through density functional theory (DFT) calculations, suggesting a chelation mechanism involving the two oxygen atoms of the phosphate group. The synthesized dendrimers, supported on the multi-walled carbon nanotubes, have shown the potential to be used for the selective toxic metal ion removal and recovery.     

Critical review of the building downwash algorithms in AERMOD

The only documentation on the building downwash algorithm in AERMOD (American Meteorological Society/U.S. Environmental Protection Agency Regulatory Model), referred to as PRIME (Plume Rise Model Enhancements), is found in the 2000 A&WMA journal article by Schulman, Strimaitis and Scire. Recent field and wind tunnel studies have shown that AERMOD can overpredict concentrations by factors of 2 to 8 for certain building configurations. While a wind tunnel equivalent building dimension study (EBD) can be conducted to approximately correct the overprediction bias, past field and wind tunnel studies indicate that there are notable flaws in the PRIME building downwash theory. A detailed review of the theory supported by CFD (Computational Fluid Dynamics) and wind tunnel simulations of flow over simple rectangular buildings revealed the following serious theoretical flaws: enhanced turbulence in the building wake starting at the wrong longitudinal location; constant enhanced turbulence extending up to the wake height; constant initial enhanced turbulence in the building wake (does not vary with roughness or stability); discontinuities in the streamline calculations; and no method to account for streamlined or porous structures.

Implications: This paper documents theoretical and other problems in PRIME along with CFD simulations and wind tunnel observations that support these findings. Although AERMOD/PRIME may provide accurate and unbiased estimates (within a factor of 2) for some building configurations, a major review and update is needed so that accurate estimates can be obtained for other building configurations where significant overpredictions or underpredictions are common due to downwash effects. This will ensure that regulatory evaluations subject to dispersion modeling requirements can be based on an accurate model. Thus, it is imperative that the downwash theory in PRIME is corrected to improve model performance and ensure that the model better represents reality.     

Apple snails and their endosymbionts bioconcentrate heavy metals and uranium from contaminated drinking water

Purpose

The differential ability of apple snail tissues, endosymbionts, and eggs to bioaccumulate several metals (Sb, As, Ba, Br, Zn, Cr, Fe, Hg, Se, and U) was investigated.

Methods

Metal concentrations were determined by neutron activation analysis in several tissues, endosymbionts, and eggs from mature apple snails cultured in either drinking water or reconstituted water (prepared with American Society for Testing and Materials type I water).

Results

The highest bioconcentration factors (BCFs) in the midgut gland were found for Ba, Zn, Se, As, U, Br, and Hg (in decreasing order), while the highest in the kidney were for Ba, Br, and Hg. The foot showed the highest BCFs for Ba, Hg, Br, and Se (in decreasing order). Calcified tissues (uterus, shell) and eggs showed low BCFs, except for Ba. Both C corpuscles and gland tissue showed statistically higher BCFs than K corpuscles for Ba, Fe, U, Br, and Sb. The concentration of most of the studied elements was significantly lower in tissues and endosymbionts obtained from snails cultured in reconstituted water instead of drinking water. Snails cultured in reconstituted water and then exposed or not to Hg, As, and U (at the maximum contaminant level allowed by the US Environmental Protection Agency) also resulted in high levels accumulated in midgut gland, endosymbionts and kidney.

Conclusions

Our findings suggest that the midgut gland (and the symbionts contained therein), the kidney, and the foot of Pomacea canaliculata may be useful bioindicators of Hg, As and U pollution in freshwater bodies and that the unrestricted use of ampullariid snails as human and animal food must be considered with caution..     

Detection of human-induced environmental disturbances in a show cave

Purpose  

We investigated the effects of human-induced disruption in a subterranean stable environment containing valuable Palaeolithic paintings and engravings (Ardales Cave, Southern Spain) using a double analytical approach.     

Global burned-land estimation in Latin America using MODIS composite data.

This paper presents results of the AQL2004 project, which has been develope within the GOFC-GOLD Latin American network of remote sensing and forest fires (RedLatif). The project intended to obtain monthly burned-land maps of the entire region, from Mexico to Patagonia, using MODIS (moderate-resolution imaging spectroradiometer) reflectance data. The project has been organized in three different phases: acquisition and preprocessing of satellite data; discrimination of burned pixels; and validation of results. In the first phase, input data consisting of 32-day composites of MODIS 500-m reflectance data generated by the Global Land Cover Facility (GLCF) of the University of Maryland (College Park, Maryland, U.S.A.) were collected and processed. The discrimination of burned areas was addressed in two steps: searching for "burned core" pixels using postfire spectral indices and multitemporal change detection and mapping of burned scars using contextual techniques. The validation phase was based on visual analysis of Landsat and CBERS (China-Brazil Earth Resources Satellite) images. Validation of the burned-land category showed an agreement ranging from 30% to 60%, depending on the ecosystem and vegetation species present. The total burned area for the entire year was estimated to be 153 215 km2. The most affected countries in relation to their territory were Cuba, Colombia, Bolivia, and Venezuela. Burned areas were found in most land covers; herbaceous vegetation (savannas and grasslands) presented the highest proportions of burned area, while perennial forest had the lowest proportions. The importance of croplands in the total burned area should be taken with reserve, since this cover presented the highest commission errors. The importance of generating systematic products of burned land areas for different ecological processes is emphasized.     

Radical precursors and related species from traffic as observed and modeled at an urban highway junction

Nitrous acid (HONO) and formaldehyde (HCHO) are important precursors for radicals and are believed to favor ozone formation significantly. Traffic emission data for both compounds are scarce and mostly outdated. A better knowledge of today's HCHO and HONO emissions related to traffic is needed to refine air quality models. Here the authors report results from continuous ambient air measurements taken at a highway junction in Houston, Texas, from July 15 to October 15, 2009. The observational data were compared with emission estimates from currently available mobile emission models (MOBILE6; MOVES [MOtor Vehicle Emission Simulator]). Observations indicated a molar carbon monoxide (CO) versus nitrogen oxides (NO_x) ratio of 6.01 ± 0.15 (r ² = 0.91), which is in agreement with other field studies. Both MOBILE6 and MOVES overestimate this emission ratio by 92% and 24%, respectively. For HCHO/CO, an overall slope of 3.14 ± 0.14 g HCHO/kg CO was observed. Whereas MOBILE6 largely underestimates this ratio by 77%, MOVES calculates somewhat higher HCHO/CO ratios (1.87) than MOBILE6, but is still significantly lower than the observed ratio. MOVES shows high HCHO/CO ratios during the early morning hours due to heavy-duty diesel off-network emissions. The differences of the modeled CO/NO_x and HCHO/CO ratios are largely due to higher NO_x and HCHO emissions in MOVES (30% and 57%, respectively, increased from MOBILE6 for 2009), as CO emissions were about the same in both models. The observed HONO/NO_x emission ratio is around 0.017 ± 0.0009 kg HONO/kg NO_x which is twice as high as in MOVES. The observed NO₂/NO_x emission ratio is around 0.16 ± 0.01 kg NO₂/kg NO_x, which is a bit more than 50% higher than in MOVES. MOVES overestimates the CO/CO₂ emission ratio by a factor of 3 compared with the observations, which is 0.0033 ± 0.0002 kg CO/kg CO₂. This as well as CO/NO_x overestimation is coming from light-duty gasoline vehicles.

Implications: Nitrous acid (HONO) and formaldehyde (HCHO) are important precursors for radicals that ultimately contribute to ozone formation. There still exist uncertainties in emission sources of HONO and HCHO and thus regional air quality modeling still tend to underestimate concentrations of free radicals in the atmosphere. This paper demonstrates that the latest U.S. Environmental Protection Agency (EPA) traffic emission model MOVES still shows significant deviations from observed emission ratios, in particular underestimation of HCHO/CO and HONO/NO_x ratios. Improving the performance of MOVES may improve regional air quality modeling.