Effects of acidic attack on chemical,mineralogical, and morphological properties of geomaterials

Environmental Science and Pollution Research - Exposure of geomaterials to acidic leachates may compromise their structure and functionality due to changes in physicochemical, mineralogical, and...     

Alternative methods for the pilot-scale production and characterization of chitosan nanoparticles

Environmental Science and Pollution Research - This work describes the production/characterization of low molar mass chitosan nanoparticles derived from waste shrimp shells (SSC), as well as from a...     

Evaluation of relative photonic efficiency in heterogeneous photocatalytic reactors

The evaluation of photonic efficiency in heterogeneous photocatalysis remains elusive because the number of absorbed photons is difficult to assess experimentally. The photonic efficiency of heterogeneous photocatalytic reactors depends on the reactor geometry, irradiation source, and photocatalyst properties. In this work, the relative photonic efficiency of heterogeneous photocatalytic reactors to degrade an azo dye was evaluated using phenol as the standard system. The experimental tests were carried out in a batch reactor under different conditions of pH, catalyst dosage, initial concentration, and ultraviolet (UV) lamps. The kinetics of disappearance of both phenol and azo dye were studied using the initial rate method and were described according to the Langmuir-Hinshelwood (L-H) kinetic model. It was observed that the relative photonic efficiency depends on the adsorption/desorption properties of the photocatalyst.     

Discriminating the pH toxicity to Poecilia reticulata Peters, 1859 in the Dunas Lake (Camaçari, BA, Brazil)

Toxic potential of the pH reduction to fingerlings of Poecilia reticulata, through acute toxicity bioassays, as well as the influence of increased pH on the toxicity were assessed. Acid lake samples (Dunas Lake) were collected during 19 months, and assessed with following treatments: water at local pH (+/-3.0) and samples with modified pH to 3.5, 3.8, 4.0, 4.3, 4.6, 5.0, 5.5, 6.0, and 6.5. Culture water samples with pH reduced to 3.0 were also assessed. Newborn P. reticulata were exposed during 96h, and dead/immobile organisms were counted at various time intervals during exposure (short intervals in the beginning and long towards the end). Mean results of LT(50) and confidence intervals from the Dunas Lake and control water with reduced pH were 1.36 (+/-0.48)h, and 1.03 (+/-0.50)h, respectively, with no statistical difference. Samples with increased pH showed a significant reduction in toxicity, with no toxicity detected at pH 6.0 and higher. Relationship between pH and lethal toxicity for fingerlings of P. reticulata demonstrated that pH exerted a strong effect on the survival of this species at the Dunas Lake, explaining about 80% of the toxicity observed.     

Pesticide dissipation curves in peach, pear and tomato crops in Uruguay

Dissipation curves of azoxystrobin and of the neonicotinoids acetamiprid and thiacloprid in peach; azinphos-methyl and carbaryl in pear and azoxystrobin, chlorfenapyr and chlorpyrifos in high-tunnel tomato crops were studied in the Southern region of Uruguay. An analytical methodology based on solid phase extraction (SPE) and detection by High Performance Liquid Chromatography with Diode Array Detector (HPLC/DAD) was used for acetamiprid and thiacloprid. Coupled SPE and detection by Gas Chromatography with Mass Selective Detector (GC/MSD) was used for the detection of azinphos-methyl, azoxystrobin, carbaryl, chlorfenapyr and chlorpyrifos residues. Curves were modeled mathematically with Solver program of Microsoft Excel. The best fit for acetamiprid and thiacloprid in peach was achieved with the exponential model (r(2)=0.961 and 0.944, respectively). In the case of peach fruits there is not a Maximum Residue Limit (MRL) for acetamiprid in the Codex Alimentarius, while 0.5 mg/kg is the value rated for thiacloprid. The MRLs accepted by the European Union (EU) are 0.1 mg/kg for acetamiprid and 0.3 mg/kg for thiacloprid. According to the curves determined in these experiments, thiacloprid residues 10 to 12 days after application (daa) were below the MRLs established by both sources. In the case of acetamiprid, 25 daa would be required, according to the exponential mathematical model, to get residues levels below the MRL values established by the EU. For azinphos methyl in pear, the residues detected were mathematically fitted to an exponential model (r(2)=0.999). According to it, residue levels under the MRL established by the EU (0.05 mg/kg) are gotten in our conditions in 20 daa. In plastic tunnel tomato chlorfenapyr residues were not detected from 16 daa, having the dissipation curve an exponential trend. In the same condition, there was not a decay of the azoxystrobin concentration during a 24-day trial, being it around 0.40 ± 0.05 mg/kg.     

Field sampling of soil pore water to evaluate trace element mobility and associated environmental risk

Monitoring soil pollution is a key aspect in sustainable management of contaminated land but there is often debate over what should be monitored to assess ecological risk. Soil pore water, containing the most labile pollutant fraction in soils, can be easily collected in situ offering a routine way to monitor this risk. We present a compilation of data on concentration of trace elements (As, Cd, Cu, Pb, and Zn) in soil pore water collected in field conditions from a range of polluted and non-polluted soils in Spain and the UK during single and repeated monitoring, and propose a simple eco-toxicity test using this media. Sufficient pore water could be extracted for analysis both under semi-arid and temperate conditions, and eco-toxicity comparisons could be effectively made between polluted and non-polluted soils. We propose that in-situ pore water extraction could enhance the realism of risk assessment at some contaminated sites.     

The influence of metal speciation on the bioavailability and sub-cellular distribution of cadmium to the terrestrial isopod, Porcellio dilatatus

Cadmium is a non-essential toxic metal that is able to bioaccumulate in both flora fauna and has the potential to biomagnify in some food chains. However, the form in which cadmium is presented to consumers can alter the bioavailability and possibly the internal distribution of assimilated Cd. Previous studies in our laboratory highlighted differences in Cd assimilation among isopods when they were provided with a plant-based food with either Cd biologically incorporated into plant tissue or superficially amended with ionic Cd(2+). Cd is known for its high affinity for sulphur ligands in cysteine residues which form the basis for metal-binding proteins such as metallothionein. This study compares Cd assimilation efficiency (AE) in Porcellio dilatatus fed with food amended with either cadmium cysteinate or cadmium nitrate in an examination of the influence of Cd speciation on metal bioavailability followed by an examination of the sub-cellular distribution using a centrifugal fractionation protocol. As hypothesized the AE of Cd among isopods fed with Cd(NO(3))(2) (64%, SE=5%) was higher than AE for isopods fed with Cd(Cys)(2) (20%, SE=3%). The sub-cellular distribution also depended on the Cd species provided. Those isopods fed Cd(Cys)(2) allocated significantly more Cd to the cell debris and organelles fractions at the expense of allocation to metal-rich granules (MRG). The significance of the difference in sub-cellular distribution with regard to toxicity is discussed. This paper demonstrates that the assimilation and internal detoxification of Cd is dependent on the chemical form of Cd presented to the isopod.     

Issues with ozone attainment methodology for Houston, TX

To comply with the federal 8-hr ozone standard, the state of Texas is creating a plan for Houston that strictly follows the U.S. Environmental Protection Agency's (EPA) guidance for demonstrating attainment. EPA's attainment guidance methodology has several key assumptions that are demonstrated to not be completely appropriate for the unique observed ozone conditions found in Houston. Houston's ozone violations at monitoring sites are realized as gradual hour-to-hour increases in ozone concentrations, or by large hourly ozone increases that exceed up to 100 parts per billion/hr. Given the time profiles at the violating monitors and those of nearby monitors, these large increases appear to be associated with small parcels of spatially limited plumes of high ozone in a lower background of urban ozone. Some of these high ozone parcels and plumes have been linked to a combination of unique wind conditions and episodic hydrocarbon emission events from the Houston Ship Channel. However, the regulatory air quality model (AQM) does not predict these sharp ozone gradients. Instead, the AQM predicts gradual hourly increases with broad regions of high ozone covering the entire Houston urban core. The AQM model performance can be partly attributed to EPA attainment guidance that prescribes the removal in the baseline model simulation of any episodic hydrocarbon emissions, thereby potentially removing any nontypical causes of ozone exceedances. This paper shows that attainment of all monitors is achieved when days with observed large hourly variability in ozone concentrations are filtered from attainment metrics. Thus, the modeling and observational data support a second unique cause for how ozone is formed in Houston, and the current EPA methodology addresses only one of these two causes.     

Assessment of oral bioaccessibility of arsenic in playground soil in Madrid (Spain): a three-method comparison and implications for risk assessment

Three methodologies to assess As bioaccessibility were evaluated using playground soil collected from 16 playgrounds in Madrid, Spain: two (Simplified Bioaccessibility Extraction Test: SBET, and hydrochloric acid-extraction: HCl) assess gastric-only bioaccessibility and the third (Physiologically Based Extraction Test: PBET) evaluates mouth-gastric-intestinal bioaccessibility. Aqua regia-extractable (pseudo total) As contents, which are routinely employed in risk assessments, were used as the reference to establish the following percentages of bioaccessibility: SBET - 63.1; HCl - 51.8; PBET - 41.6, the highest values associated with the gastric-only extractions. For Madrid playground soils - characterised by a very uniform, weakly alkaline pH, and low Fe oxide and organic matter contents - the statistical analysis of the results indicates that, in contrast with other studies, the highest percentage of As in the samples was bound to carbonates and/or present as calcium arsenate. As opposed to the As bound to Fe oxides, this As is readily released in the gastric environment as the carbonate matrix is decomposed and calcium arsenate is dissolved, but some of it is subsequently sequestered in unavailable forms as the pH is raised to 5.5 to mimic intestinal conditions. The HCl extraction can be used as a simple and reliable (i.e. low residual standard error) proxy for the more expensive, time consuming, and error-prone PBET methodology. The HCl method would essentially halve the estimate of carcinogenic risk for children playing in Madrid playground soils, providing a more representative value of associated risk than the pseudo-total concentrations used at present.     

Frequency of micronuclei and of other nuclear abnormalities in erythrocytes of the grey mullet from the Mondego,Douro and Ave estuaries—Portugal

Fish are bioindicators of water pollution, and an increased rate of their erythrocyte nuclear morphological abnormalities (ENMAs)—and particularly of erythrocyte micronuclei (EMN)—is used as a genotoxicity biomarker. Despite the potential value of ENMAs and MN, there is scarce information about fish captured in Iberian estuaries. This is the case of the Portuguese estuaries of the Mondego, Douro and Ave, suffering from different levels of environmental stress and where chemical surveys have been disclosing significant amounts of certain pollutants. So, the aim of this study was to evaluate genotoxicants impacts and infer about the exposure at those ecosystems, using the grey mullet (Mugil cephalus) as bioindicator and considering the type and frequency of nuclear abnormalities of erythrocytes as proxies of genotoxicity. Sampling of mullets was done throughout the year in the important Mondego, Douro and Ave River estuaries (centre and north-western Portugal). The fish (total n?=?242) were caught in campaigns made in spring–summer and autumn–winter, using nets or fishing rods. The sampled mullets were comparable between locations in terms of the basic biometric parameters. Blood smears were stained with Diff-Quik to assess the frequencies of six types of ENMAs and MN (given per 1,000 erythrocytes). Some basic water physicochemical parameters were recorded to search for fluctuations matching the ENMAs. Overall, the most frequent nucleus abnormality was the polymorphic type, sequentially followed by the blebbed/lobed/notched, segmented, kidney shaped, vacuolated, MN and binucleated. The total average frequency of the ENMAs ranged from 73?‰ in the Mondego to 108?‰ in the Ave. The polymorphic type was typically ≥50 % of the total ENMAs, averaging about 51?‰, when considering all three estuaries. The most serious lesion—the MN—in fish from Mondego and Douro had a similar frequency (≈0.38?‰), which was significantly lower than that in the Ave (0.75?‰). No significant seasonal differences existed as to the MN rates and seasonal differences existed almost only in the Douro, with the higher values in AW. In general, the pattern of ENMAs frequencies was unrelated with the water physicochemical parameters. Considering the data for both the total ENMAs and for each specific abnormality, and bearing in mind that values of MN in fish erythrocytes >0.3?‰ usually reflect pollution by genotoxicants, it is suggested that mullets were likely being chronically exposed to such compounds, even in the allegedly less polluted ecosystem (Mondego). Moreover, data supported the following pollution exposure gradient: Mondego?<?Douro?<?Ave. The scenario and inferences nicely agree with the published data from chemical monitoring.