Metal mobility during in situ chemical oxidation of TCE by KMnO4

The potential for trace-metal contamination of aquifers as a side effect of In Situ Chemical Oxidation (ISCO) of chlorinated solvent contamination by KMnO(4) is investigated with column experiments. The experiments investigate metal mobility during in situ chemical oxidation of TCE by KMnO(4) under conditions where pH, flow rate, KMnO(4), TCE, and trace-metal concentrations were controlled. During ISCO, the injection of MnO(4) creates oxidizing conditions, and acidity released by the reactions causes a tendency toward low pH in aquifers. In order to evaluate the role of pH buffering on metal mobility, duplicate columns were constructed, one packed with pure silica sand, and one with a mixture of silica sand and calcite. Aqueous solutions of TCE and KMnO(4) (with 1 mg/L Cu, Pb, Zn, Mo, Ni, and Cr(VI)) were allowed to mix at the inlet to the columns. After the completion of the experiments, samples of Mn oxide were removed from the columns and analyzed by analytical scanning and transmission electron microscopy. In order to relate the results of the laboratory experiments to field settings, the analyses of Mn-oxide samples from the lab experiments were compared to samples of Mn oxide collected from a field-scale chemical-oxidation experiment that were also analyzed by analytical electron microscopy as well as time-of-flight secondary-ion mass spectroscopy. The pH ranged from 2.40 in the silica sand column to 6.25 in the calcite-containing column. The data indicate that aqueous Mo, Pb, Cu and Ni concentrations are attenuated almost completely within the columns. In contrast, Zn concentrations are not significantly attenuated and Cr(VI) is transported conservatively. The results indicate that within the range 2.40 to 6.25, metal mobility is not affected by pH. Comparison of analyses of Mn-oxide from the lab and field demonstrate that a variety of metals are sequestered from solution by Mn oxide.     

Remediation efficiency of vapour extraction of sandy soils contaminated with cyclohexane: Influence of air flow rate, water and natural organic matter content

This work reports the analysis of the efficiency and time of soil remediation using vapour extraction as well as provides comparison of results using both, prepared and real soils. The main objectives were: (i) to analyse the efficiency and time of remediation according to the water and natural organic matter content of the soil; and (ii) to assess if a previous study, performed using prepared soils, could help to preview the process viability in real conditions. For sandy soils with negligible clay content, artificially contaminated with cyclohexane before vapour extraction, it was concluded that (i) the increase of soil water content and mainly of natural organic matter content influenced negatively the remediation process, making it less efficient, more time consuming, and consequently more expensive; and (ii) a previous study using prepared soils of similar characteristics has proven helpful for previewing the process viability in real conditions.     

Synthesis of zirconia-immobilized copper chelates for catalytic decomposition of hydrogen peroxide and the oxidation of polycyclic aromatic hydrocarbons

Chelating sorbents with diethylenetriaminepenta(methylene-phosphonic acid) (DTPMPA) and ethylenediaminetetraacetic acid ligands immobilized on zirconia matrix were prepared and subsequently saturated with Cu(II). All the Cu chelates catalyzed decomposition of H(2)O(2) yielding highly reactive hydroxyl radicals. All of them were also able to catalyze degradation of polycyclic aromatic hydrocarbons (anthracene, benzo[a]pyrene and benzo[b]fluoranthene). The most effective DTPMPA-based catalysts G-32 and G-35 (10 mg ml(-1) with 100 mmol H(2)O(2)) caused almost complete decomposition of 15 ppm anthracene and benzo[a]pyrene during a five day catalytic cycle at 30 degrees C. Anthracene-1,4-dione was the main product of anthracene oxidation by all catalysts. The catalysts were active in several cycles without regeneration.     

Perioperative fetal hemodynamic changes in twin-twin transfusion syndrome and neurodevelopmental outcome at two years of age

Objective

To investigate whether perioperative fetal hemodynamic changes in twin-to-twin transfusion syndrome (TTTS) are associated with neurodevelopmental impairment (NDI) at two years.

Methods

Doppler parameters of three sonograms (day before, first day after and 1 week after laser surgery for TTTS) were assessed for correlation with neurodevelopmental outcome at two years (2008-2016). NDI was defined as: cerebral palsy, deafness, blindness, and/or a Bayley-III cognitive/motor developmental test-score > 2SD below the mean.

Results

Long-term outcome was assessed in 492 TTTS survivors. NDI was present in 5% (24/492). After adjustment for severe cerebral injury (present in 4%), associated with NDI were: middle cerebral artery peak systolic velocity (MCA-PSV) >1.5 multiples of the median (MoM) 1 day after surgery (odds ratio [OR] 4.96; 95% confidence interval [CI]: 1.17-21.05, P = .03), a change from normal umbilical artery pulsatility index (UA-PI) presurgery to UA-PI >p95 postsurgery (OR 4.19; 95% CI: 1.04-16.87, P = .04), a change from normal to MCA-PSV >1.5MoM (OR 4.75; 95% CI: 1.43-15.77, P = .01).

Conclusion

Perioperative fetal hemodynamic changes in TTTS pregnancies treated with laser are associated with poor neurodevelopmental outcome. Prospective research on the cerebrovascular response to altered hemodynamic conditions is necessary to further understand the cerebral autoregulatory capacity of the fetus in relation to neurodevelopmental outcome.     

Evolution rates and PCB content of surface films that develop on impervious urban surfaces

Surface films on impervious surfaces mediate the fate of organic contaminants in urban areas. Using sheltered 3-mm diameter glass beads as a surrogate impervious urban surface, studies in downtown Toronto showed that surface films developed at a consistent rate of 1.6–2.6 nm day⁻¹. Linear film growth was observed up to and including the last day of three studies of 89-, 273-, and 84-day duration. Total PCB content (sum of 15 PCB congeners) also increased linearly, at a similar rate as the surface film. A complementary study using unsheltered beads showed that up to 80% of film mass and PCB content were removed by film wash-off during rain events. The film growth rate on beads exposed at a rural site, 200 km northeast of Toronto, was 12–20 times lower with PCB burdens that were 7–22 times lower compared to Toronto. Based on these findings, it is estimated that approximately 56–226 g of PCBs are captured by a 70 nm thick film covering just the horizontal surface area of Toronto. This is a substantial quantity of PCB that is available for rapid surface–air exchange and wash-off.     

When does nitrate become a risk for humans?

Is nitrate harmful to humans? Are the current limits for nitrate concentration in drinking water justified by science? There is substantial disagreement among scientists over the interpretation of evidence on the issue. There are two main health issues: the linkage between nitrate and (i) infant methaemoglobinaemia, also known as blue baby syndrome, and (ii) cancers of the digestive tract. The evidence for nitrate as a cause of these serious diseases remains controversial. On one hand there is evidence that shows there is no clear association between nitrate in drinking water and the two main health issues with which it has been linked, and there is even evidence emerging of a possible benefit of nitrate in cardiovascular health. There is also evidence of nitrate intake giving protection against infections such as gastroenteritis. Some scientists suggest that there is sufficient evidence for increasing the permitted concentration of nitrate in drinking water without increasing risks to human health. However, subgroups within a population may be more susceptible than others to the adverse health effects of nitrate. Moreover, individuals with increased rates of endogenous formation of carcinogenic N-nitroso compounds are likely to be susceptible to the development of cancers in the digestive system. Given the lack of consensus, there is an urgent need for a comprehensive, independent study to determine whether the current nitrate limit for drinking water is scientifically justified or whether it could safely be raised.     

Daily Updating of Operational Statistical Seasonal Water Supply Forecasts for the western U.S.1

Abstract: Official seasonal water supply outlooks for the western United States are typically produced once per month from January through June. The Natural Resources Conservation Service has developed a new outlook product that allows the automated production and delivery of this type of forecast year‐round and with a daily update frequency. Daily snow water equivalent and water year‐to‐date precipitation data from multiple SNOTEL stations are combined using a statistical forecasting technique (“Z‐Score Regression”) to predict seasonal streamflow volume. The skill of these forecasts vs. lead‐time is comparable to the official published outlooks. The new product matches the intra‐monthly trends in the official forecasts until the target period is partly in the past, when the official forecasts begin to use information about observed streamflows to date. Geographically, the patterns of skill also match the official outlooks, with highest skill in Idaho and southern Colorado and lowest skill in the Colorado Front Range, eastern New Mexico, and eastern Montana. The direct and frequent delivery of objective guidance to users is a significant new development in the operational hydrologic seasonal forecasting community.     

Lagoon-biogas emissions and carbon balance estimates of a swine production facility

Gaseous emissions from animal manure storage facilities can contribute to global greenhouse gas inventories. Biogas fluxes were measured for one year from a 2-ha anaerobic lagoon that received waste from a 10500-head swine (Sus scrofa) finishing operation in southwestern Kansas. During 2001, ebullition of biogas was measured continuously by using floating platforms equipped with gas-collection domes. Periodically, the composition of the biogas was determined by using gas chromatography. Detailed records of feed quality and quantity and animal weights and gains also were obtained to determine the carbon budget of the facility (barns and lagoon). Flux of biogas was very seasonal, with peak emission (18.7 mol m(-2) d(-1)) occurring in early June. Nearly 50% of the annual biogas losses occurred during a 30-d period beginning on day of year (DOY) 146. Flux patterns suggest that the start of the high biogas production period was governed by temperature, while the decline in production in mid-June was caused by substrate limitations. Average biogas composition was 0.71 L CH4 L(-1). The quantity of CH4 released from the lagoon was 86.3 Mg yr(-1), which represents about 38 g of CH4 per kg of animal weight gain. The average flux density of biogas from the lagoon was 382 mol m(-2) yr(-1) or 728 mol yr(-1) per resident animal where the resident animal population was 10500. Flux rates of CH4 were 1.7 to 3.4 times less than predictions made with Intergovernmental Panel on Climate Change (IPCC) models. Additional research is needed on the carbon budgets of other animal feeding operations so that better estimates of greenhouse gas emissions can be determined.     

Modelling soil series data to facilitate targeted habitat restoration: a polytomous logistic regression approach

Habitat restoration at a landscape scale is becoming increasingly important in environmental management. In this context, geographical information systems are well suited as they can store and integrate many of the abiotic and biotic criteria used to assess the ecological worth of a site. However, this capacity can be limited by the availability or suitability of spatial data sets. A classic example of the latter case is the National Soil Map of England and Wales, which groups soils of a varied nature into associations. Consequently the national soil map has proved to be a poor predictor of habitat suitability. Using polytomous logistic regression we put forward a method for separating soil associations into their constituent soils within the Chilterns Natural Area. This approach used soil association, aspect, slope and relative height as variables for this analysis. Whilst the model's performance is likely to have been limited by the accuracy of the soil association data set, a predictive accuracy of between 47 and 65% is sufficient to facilitate better targeting of habitat restoration when combined with other abiotic factors such as climate and topography.