Use of a reactive transport model to describe reductive dechlorination (RD) as a remediation design tool: application at a CAH-contaminated site

In this paper, a numerical model is presented that is capable of describing the complex set of biochemical processes that occur in chlorinated aliphatic hydrocarbon (CAH)-contaminated groundwater when an exogenous electron donor is added. The reactive pattern is based on the degradation pathways of both chlorinated ethanes and ethenes, and it includes electron donor production (H₂ and acetate) from the fermentation of an organic substrate as well as rate-limiting processes related to electron acceptor competition. Coupling of the kinetic model to a convection–dispersion module is described. The calibration phase was carried out using data obtained at a real CAH-contaminated site in the north of Italy. Model simulations of different application scenarios are presented to draw general conclusions on the effectiveness of reductive dechlorination (RD) as a possible cleanup strategy. Early outcomes indicate that cleanup targets can only be achieved if source longevity is reduced. Therefore, metabolic RD is expected to produce beneficial effects because it is known to induce bioenhanced degradation and transformation of CAHs.     

Determination of dimethyl fumarate (DMFu) in silica gel pouches using gas chromatography coupled ion trap mass spectrometry

A simple method for the determination of dimethyl fumarate (DMFu) in silica gel pouches has been developed. The gas chromatographic behaviour of DMFu was investigated; the instrumental method, based on EI mass spectrometry coupled with an Ion Trap Detector operating whether in full scan mode or in MS/MS mode was also investigated. Several factors have been evaluated and optimized during the development process: solvent and temperature of extraction, type of stationary phase in capillary column. The analytical procedure consists of two steps as follows: (a) the sample preparation using 10 g of sample extracted with acetonitrile in an ultrasonic, heated bath and (b) the determination by gas chromatography-ion trap mass spectrometry. Mass spectrometry in conjunction with chromatographic separation is a very powerful combination for identification of an analyte in the extract in spite of selective detectors employed with GC, such as ECD, FPD and NPD, that offer only limited specificity. Blank samples show no interfering peaks in the areas of interest, so the specificity of the method was assured under the investigated GC/MS conditions. The method has been validated in terms of recovery, repeatability, linearity, detection limits and measurement uncertainty. The results obtained meet both the method validation criteria and requirements of the European/National legislation. The method was verified to be accurate with 97 % mean recoveries at 0.05 mg/kg and 1.00 mg/kg levels; the repeatability (expressed as RSD %) was found to be better than 15 %. Good linearity was found in the range between 0.05 μg/mL and 5.0 μg/mL and a value of R2 > 0.9998 was calculated. The procedure ensures high specificity and a good sensitivity with detection limit (ld) of 0.02 mg/kg and quantification limit (LOQ) of 0.05 mg/kg. This procedure has been successfully applied for the analysis of several hundred of real samples collected during a monitoring control plan started last year in our country. All samples exceeding the maximum allowed level of DMFu (0, 1 mg/kg) were confirmed by GC/MS/MS (ITD) for a higher degree of confidence in identification. The main advantages of this method include: rapidity, simplicity (few, simple steps), reliability, cheapness, no need for long and difficult clean-up and evaporation steps, high specificity by using GC/MS and GC/MS/MS, availability for routine monitoring.     

Anammox: an option for ammonium removal in bioreactor landfills

Experiments carried out in bioreactor landfill simulators demonstrated that more than 40% of the total N was transferred into the liquid and gas phases during the incubation period of 380 days. Ammonium, an end product of protein degradation and important parameter to consider during landfill closure, tends to accumulate up to inhibitory levels in the leachate of landfills especially in landfills with leachate recirculation. Most efforts to remove ammonium from leachate have been focused on ex situ and partial in situ methods such as nitrification, denitrification and chemical precipitation. Besides minimal contributions from other N-removal processes, Anammox (Anaerobic Ammonium Oxidation) bacteria were found to be active within the simulators. Anammox is considered to be an important contributor to remove N from the solid matrix. However, it was unclear how the necessary nitrite for Anammox metabolism was produced. Moreover, little is known about the nature of residual nitrogen in the waste mass and possible mechanisms to remove it. Intrusion of small quantities of O₂ is not only beneficial for the degradation process of municipal solid waste (MSW) in bioreactor landfills but also significant for the development of the Anammox bacteria that contributed to the removal of ammonium. Volatilisation and Anammox activity were the main N removal mechanisms in these pilot-scale simulators. The results of these experiments bring new insights on the behaviour, evolution and fate of nitrogen from solid waste and present the first evidence of the existence of Anammox activity in bioreactor landfill simulators.     

Mercury, lead and cadmium in human milk in relation to diet, lifestyle habits and sociodemographic variables in Madrid (Spain)

Background

Although breastfeeding is the ideal way of nurturing infants, it can be a source of exposure to toxicants. This study reports the concentration of Hg, Pb and Cd in breast milk from a sample of women drawn from the general population of the Madrid Region, and explores the association between metal levels and socio-demographic factors, lifestyle habits, diet and environmental exposures, including tobacco smoke, exposure at home and occupational exposures.

Methods

Breast milk was obtained from 100 women (20 mL) at around the third week postpartum. Pb, Cd and Hg levels were determined using Atomic Absorption Spectrometry. Metal levels were log-transformed due to non-normal distribution. Their association with the variables collected by questionnaire was assessed using linear regression models. Separate models were fitted for Hg, Pb and Cd, using univariate linear regression in a first step. Secondly, multivariate linear regression models were adjusted introducing potential confounders specific for each metal. Finally, a test for trend was performed in order to evaluate possible dose-response relationships between metal levels and changes in variables categories.

Results

Geometric mean Hg, Pb and Cd content in milk were 0.53 μg L⁻¹, 15.56 μg L⁻¹, and 1.31 μg L⁻¹, respectively. Decreases in Hg levels in older women and in those with a previous history of pregnancies and lactations suggested clearance of this metal over lifetime, though differences were not statistically significant, probably due to limited sample size. Lead concentrations increased with greater exposure to motor vehicle traffic and higher potato consumption. Increased Cd levels were associated with type of lactation and tended to increase with tobacco smoking.

Conclusions

Surveillance for the presence of heavy metals in human milk is needed. Smoking and dietary habits are the main factors linked to heavy metal levels in breast milk. Our results reinforce the need to strengthen national food safety programs and to further promote avoidance of unhealthy behaviors such as smoking during pregnancy.     

Recreation demand analysis under truncation, overdispersion, and endogenous stratification: an application to Gros Morne National Park

Using on-site survey data from Gros Morne National Park in Newfoundland, this paper estimates and compares several truncated count data models of recreation demand. The selected model accounts not only for the truncated and overdispersed nature of the data but also for endogenous stratification due to the oversampling of avid users. Moreover, the model that allows for a flexible specification of the overdispersion parameter dominates on the basis of goodness of fit. The results are used to estimate the users' value of access to the park.     

Historical decline in coral reef growth after the Panama Canal

The Panama Canal is near its vessel size and tonnage handling capacity, and Panamanians have decided to expand it. The expansion of the Canal may consider the historical long-lasting impacts on marine coastal habitats particularly on sensitive coral reefs. These potential impacts were discussed during the national referendum as were other equally important issues, such as its effects on forests, watersheds, and water supply. Coral growth rates provide a direct measure of coral fitness and past environmental conditions comparable to analyses of tree rings. We examined stable isotopes, metal geochemical tracers, and growth rates on a century-long (1880-1989) chronology based on 77 cores of the dominant reef-building coral Siderastrea siderea collected near the Caribbean entrance to the canal. Our results showed a gradual decline in coral growth unrelated to changes in sea surface temperature but linked to runoff and sedimentation to coastal areas resulting from the construction and operation of the Panama Canal.     

Arsenic removal from water employing heterogeneous photocatalysis with TiO2 immobilized in PET bottles

Arsenic oxidation (As(III) to As(V)) and As(V) removal from water were assessed by using TiO₂ immobilized in PET (polyethylene terephthalate) bottles in the presence of natural sunlight and iron salts. The effect of many parameters was sequentially studied: TiO₂ concentration of the coating solution, Fe(II) concentration, pH, solar irradiation time; dissolved organic carbon concentration. The final conditions (TiO₂ concentration of the coating solution: 10%; Fe(II): 7.0 mg l⁻¹; solar exposure time: 120 min) were applied to natural water samples spiked with 500 μg l⁻¹ As(III) in order to verify the influence of natural water matrix. After treatment, As(III) and total As concentrations were lower than the limit of quantitation (2 μg l⁻¹) of the voltammetric method used, showing a removal over 99%, and giving evidence that As(III) was effectively oxidized to As(V). The results obtained demonstrated that TiO₂ can be easily immobilized on a PET surface in order to perform As(III) oxidation in water and that this TiO₂ immobilization, combined with coprecipitation of arsenic on Fe(III) hydroxides(oxides) could be an efficient way for inorganic arsenic removal from groundwaters.     

Arsenate tolerance in Silene paradoxa does not rely on phytochelatin-dependent sequestration

Arsenate tolerance, As accumulation and As-induced phytochelatin accumulation were compared in populations of Silene paradoxa, one from a mine site enriched in As, Cu and Zn, the other from an uncontaminated site. The mine population was significantly more arsenate-tolerant. Arsenate uptake and root-to-shoot transport were slightly but significantly higher in the non-mine plants. The difference in uptake was quantitatively insufficient to explain the difference in tolerance between the populations. As accumulation in the roots was similar in both populations, but the mine plants accumulated much less phytochelatins than the non-mine plants. The mean phytochelatin chain length, however, was higher in the mine population, possibly due to a constitutively lower cellular glutathione level. It is argued that the mine plants must possess an arsenic detoxification mechanism other than arsenate reduction and subsequent phytochelatin-based sequestration. This alternative mechanism might explain at least some part of the superior tolerance in the mine plants.     

Multi-objective optimization of solid waste flows: environmentally sustainable strategies for municipalities

An approach to sustainable municipal solid waste (MSW) management is presented, with the aim of supporting the decision on the optimal flows of solid waste sent to landfill, recycling and different types of treatment plants, whose sizes are also decision variables. This problem is modeled with a non-linear, multi-objective formulation. Specifically, four objectives to be minimized have been taken into account, which are related to economic costs, unrecycled waste, sanitary landfill disposal and environmental impact (incinerator emissions). An interactive reference point procedure has been developed to support decision making; these methods are considered appropriate for multi-objective decision problems in environmental applications. In addition, interactive methods are generally preferred by decision makers as they can be directly involved in the various steps of the decision process. Some results deriving from the application of the proposed procedure are presented. The application of the procedure is exemplified by considering the interaction with two different decision makers who are assumed to be in charge of planning the MSW system in the municipality of Genova (Italy).     

Depletion of selected polychlorinated biphenyl, dibenzodioxin, and dibenzofuran congeners in farmed rainbow trout (Oncorhynchus mykiss): a hint for safer fish farming

Farmed fish can be exposed to persistent organic contaminants--such as polychlorinated biphenyls (PCBs), dibenzodioxins (PCDDs), and dibenzofurans (PCDFs)--via feed, this eventually resulting in accumulation levels of health concern. To study the correlation between feed contamination, chemical accumulation in fish muscle (fillet), and chemical depletion, an all-vegetal base (or blank) feed was prepared and fortified with a commercial PCB mixture (Aroclor 1254) and six PCDD and PCDF congeners (namely, 2,3,7,8-T(4)CDD, 2,3,7,8-T(4)CDF, 1,2,3,7,8-P(5)CDD, 1,2,3,7,8-P(5)CDF, O(8)CDD, and O(8)CDF) to reproduce realistic low, medium, and high contamination levels. After a 1-month exposure, trout (Oncorhynchus mykiss) were fed with the blank feed and sacrificed every 0.5 months over a 3-month period from exposure end; fillet specimens were sampled at each time. In all groups, the average fish weight increased linearly through the observation period. The chemical diminishing patterns observed were due to the combined effect of clearance and growth dilution: for 10 PCB and four PCDD and PCDF congeners, patterns were described with an empirical one-compartment (fish muscle) model. The canonical pseudo-first-order kinetic equation used was also modified into the form C=[C(0)exp(-k(C)t)] (m(W)t+1)(-1) to distinguish between the contributions to depletion from clearance, exp(-k(C)t), and growth dilution, (m(W)t+1)(-1). Most mean clearance half-life (HL(C)) estimates appear to be greater than 4 months, in a number of cases reaching magnitudes well over 10 months or even negative, thus clearly indicating a non-negligible contribution from a second compartment. Based on means and their 95% confidence intervals, the depletion HL(D) estimates of the 14 selected congeners seem to be comprised between 1.2-3.4 and 1.0-5.0 months, respectively: these values, accounting for both clearance and growth dilution, provide an indication of the relevance of a blank feed as a management option to reduce the overall PCB, PCDD, and PCDF content in farmed trout. Due to a lack of bioaccumulation, O(8)CDD and O(8)CDF yielded no results for evaluation, whereas for many PCB congeners results were insufficient for empirical modelling.