Rapid reductive dechlorination of atrazine by zero-valent iron under acidic conditions

The dechlorination of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) via reaction with metallic iron under low-oxygen conditions was studied using reaction mixture pH values of 2.0, 3.0, and 3.8. The pH control was achieved through addition of sulfuric acid throughout the duration of the reaction. The lower the pH of the reaction mixture, the faster the degradation of atrazine. The surface area of the sulfuric acid-treated iron particles was 0.31 (+/- 0.01) m2 g-1 and the surface area normalized initial pseudo-first order rate constants (kSA, where rate = kSA x (surface area/l) x [Atrazine]) at pH values of 2.0, 3.0, and 3.8 were equal to, respectively, 3.0 (+/- 0.4) x 10(-3) min-1 m-2 l, 5 (+/- 3) x 10(-4) min-1 m-2 l, and 1 (+/- 1) x 10(-4) min-1 m-2 l. The observed products of the degradation reaction were dechlorinated atrazine (2-ethylamino-4-isopropylamino-1,3,5-triazine) and possibly hydroxyatrazine (2-ethylamino-4-isopropylamino-6-hydroxy-s-triazine). Triazine ring protonation may account, at least in part, for the observed effect of pH on atrazine dechlorination via metallic iron.     

RESERVOIR MANAGEMENT RULES DERWED WITH THE AID OF MULTIPLE OBJECTIVE DECISION MAKING TECHNIQUES1

ABSTRACT: The determination of optimum reservoir operating rules for reservoirs with multiple conflicting objectives is still a difficult task - despite many publications in this field. In this paper a three-step Multi Objective Decision Making (MODM) method is presented, the emphasis of which is placed on the necessity to make the work easy for the decision maker, which many MODM techniques fail to achieve. The method is applied to the development of a compromise optimum operating rule for a multi-purpose reservoir. In the first step of the method stochastic DP is chosen which is combined with the “weighting method” allowing combination of various objectives into one objective function. By systematically varying the weights for the objectives a large number of pareto optimum reservoir operating rules is generated. In the second step of the method the performance of all these operating rules is tested with the aid of a model simulating reservoir operation. The results are statistically analyzed and the reliabilities for attaining the various objectives are computed. The third step of the model applies another MODM technique which allows the decision maker - in a computer dialog - to select his optimum reservoir operating rule from the large number of pareto optimum solutions generated in step 1. Here he can specify his preferences for the various objectives. For this purpose two alternative MODM techniques are offered: Compromise Programming and the SEMOPS method. Their performance is shown along with the generation and selection of operating rules for the multi-objective Wupper reservoir system in Germany.     

CONTROL OF NATURAL BRINE SPRINGS IN BRAZOS RIVER BASIN PART II: BRINE DISPOSAL1

ABSTRACT: Water quality in the Brazos River of Texas is seriously degraded by natural salt pollution. Two thousand tons/day of total dissolved solids emanate from brine springs and seeps in the Upper Brazos River drainage. Approximately 45 percent of the total salt load comes from a relatively small flow in the Dove Creek area. The companion paper demonstrates that a system of wells pumping brine at a constant rate of about 2 cfs from the near surface aquifer should eliminate the brine springs in this area. In this paper, injection into deep brine aquifers is shown to be a feasible brine disposal alternative. Four brine aquifers were determined from the literature to be possible injection zones. Accurate net aquifer thickness maps were generated in a 23 by 14 mile area centered on the Dove Creek area for three of the aquifers from an interpretation of 41 well logs. Constant injection for a project life of 100 years was simulated using the SWIFT/486 software. Modeling suggests that one well would be sufficient to inject the entire disposal volume into either the Strawn or Ellenburger Formation.     

Evaluation of biodegradation of nonylphenol ethoxylate and lignin by combining toxicity assessment and chemical characterization

The aerobic biodegradation of commercial nonylphenol ethoxylate (NPE) mixture and alkali lignin was studied using the OECD headspace test accompanied by the simultaneous measurement of ecotoxicity directly from the biodegradation liquors and by the follow-up of the chemical composition of the studied chemicals. NPE degradation was dependent on the inoculum source: approximately 40% of NPE was mineralized into CO₂ during the 4-week experiment when inoculum from Helsinki City wastewater treatment plant (WWTP) was used, and only 12% was mineralized when inoculum from Jyväskylä City WWTP was used. Chemical analyses revealed a shift in the ethoxylate chain length from longer to shorter soon after the beginning of the NPE biodegradation tests. At the same time also toxicity (reverse electron transport assay, RET) and estrogenic activity (human estrogen receptor yeast) measured directly from the biodegradation liquors decreased. In case of alkali lignin, approximately 11% was mineralized in the test and chemical analysis showed in maximum a 30% decrease in lignin concentration. Toxicity of lignin biodegradation liquors started to decrease in the beginning of the test, but became more toxic towards the end of the test again. Especially RET assay proved to be sensitive enough for measuring toxicity changes directly from biodegradation liquors, although a concentrating treatment of the liquors is recommended for a more detailed characterization and identification of toxic metabolites.     

Non-linear incentives,plan design,and flood mitigation: the case of the Federal Emergency Management Agency's community rating system

A basic proposition of ‘agency theory’ is that output-based performance incentives encourage greater effort. However, studies find that incentive schemes can distort effort if rewards for performance are discrete or non-linear. The Federal Emergency Management Agency's (FEMA) Community Rating System (CRS) is a flood mitigation programme with a non-linear incentive design. Under this programme, localities are incentivised to implement a mix of 18 flood mitigation activities. Each activity is performance scored, with accumulated scores corresponding to a percent discount on flood insurance premiums for residents that hold National Flood Insurance policies. Discounts range from 0 to 45% and increase discretely in increments of 5%. With multivariate statistical and Geographic Information Systems analytic techniques, tests are made to find whether observed changes in annual CRS scores for participating localities in Florida are explained by non-linear incentives, adjusting for hydrologic conditions, flood disaster histories, socio-economic and human capital controls that can plausibly account for local mitigation activity scores over time. Results indicate that local jurisdictions are discount-seeking, with mitigation efforts partially driven by the non-linear incentive design of the CRS programme. The paper ends with recommendations to improve the operation FEMA's flood mitigation programme.     

Household adjustment to flood risk: a survey of coastal residents in Texas and Florida,United States

Individual households have increasingly borne responsibility for reducing the adverse impacts of flooding on their property. Little observational research has been conducted, however, at the household level to examine the major factors contributing to the selection of a particular household adjustment. This study addresses the issue by evaluating statistically the factors influencing the adoption of various household flood hazard adjustments. The results indicate that respondents with higher‐value homes or longer housing tenure are more likely to adopt structural and expensive techniques. In addition, the information source and the Community Rating System (CRS) score for the jurisdiction where the household is located have a significant bearing on household adjustment. In contrast, proximity to risk zones and risk perception yield somewhat mixed results or behave counter to assumptions in the literature. The study findings provide insights that will be of value to governments and decision‐makers interested in encouraging homeowners to take protective action given increasing flood risk.     

Effects of Lawn Maintenance on Nutrient Losses Via Overland Flow During Natural Rainfall Events1

Spence, Porchè L., Deanna L. Osmond, Wesley Childres, Joshua L. Heitman, and Wayne P. Robarge, 2012. Effects of Lawn Maintenance on Nutrient Losses Via Overland Flow During Natural Rainfall Events. Journal of the American Water Resources Association (JAWRA) 48(5): 909‐924. DOI: 10.1111/j.1752‐1688.2012.00658.x Abstract: A sampling system was used to evaluate the effect of residential lawn management on nutrient losses via overland flow generated during natural rainfall events from three residential landscapes: a high maintenance fescue lawn (HMFL), a low maintenance fescue lawn (LMFL), and a mixed forested residential landscape (FRL). A sampling system was located in designated areas within each landscape such that 100% of the runoff follows natural flow paths to the outlet ports and collects in sterile Nalgene^® B³ media bags (Thermo Fisher Scientific, Rochester, NY). A rainfall event was defined as producing ≥2.54 mm of water. A total of 87 rainfall events occurred during a 20‐month monitoring period. The total runoff volume collected from the LMFL was higher than from the HMFL and FRL, but on average <1% of the total rainfall was collected from the three landscapes. Mean nitrate concentrations from each lawn did not exceed 0.6 mg N/l. Nutrient unit area losses from the HMFL, LMFL, and FRL were 1,000 times less than fertilizer and throughfall inputs, which were due to the presence of well‐structured soils (low bulk densities) with high infiltration rates. This study demonstrated that the frequency of runoff, total runoff volumes, and nutrient losses during natural rainfall events are lower from highly maintained (i.e., irrigation, fertilizer application, and reseeding) densely uniform manicured lawns than low maintenance lawns and forested residential landscapes.     

Regression models for estimating concentrations of atrazine plus deethylatrazine in shallow groundwater in agricultural areas of the United States

Tobit regression models were developed to predict the summed concentration of atrazine [6-chloro--ethyl--(1-methylethyl)-1,3,5-triazine-2,4-diamine] and its degradate deethylatrazine [6-chloro--(1-methylethyl)-1,3,5,-triazine-2,4-diamine] (DEA) in shallow groundwater underlying agricultural settings across the conterminous United States. The models were developed from atrazine and DEA concentrations in samples from 1298 wells and explanatory variables that represent the source of atrazine and various aspects of the transport and fate of atrazine and DEA in the subsurface. One advantage of these newly developed models over previous national regression models is that they predict concentrations (rather than detection frequency), which can be compared with water quality benchmarks. Model results indicate that variability in the concentration of atrazine residues (atrazine plus DEA) in groundwater underlying agricultural areas is more strongly controlled by the history of atrazine use in relation to the timing of recharge (groundwater age) than by processes that control the dispersion, adsorption, or degradation of these compounds in the saturated zone. Current (1990s) atrazine use was found to be a weak explanatory variable, perhaps because it does not represent the use of atrazine at the time of recharge of the sampled groundwater and because the likelihood that these compounds will reach the water table is affected by other factors operating within the unsaturated zone, such as soil characteristics, artificial drainage, and water movement. Results show that only about 5% of agricultural areas have greater than a 10% probability of exceeding the USEPA maximum contaminant level of 3.0 μg L. These models are not developed for regulatory purposes but rather can be used to (i) identify areas of potential concern, (ii) provide conservative estimates of the concentrations of atrazine residues in deeper potential drinking water supplies, and (iii) set priorities among areas for future groundwater monitoring.     

Comparative embryotoxicity of a pentabrominated diphenyl ether mixture to common terns (Sterna hirundo) and American kestrels (Falco sparverius)

Concentrations of polybrominated diphenyl ethers (PBDEs) in Forster’s tern (Sterna forsteri) eggs from San Francisco Bay have been reported to range up to 63 μg g⁻¹ lipid weight. This value exceeds the lowest-observed-adverse-effect level (1.8 μg g⁻¹ egg wet weight; ∼32 μg⁻¹ lipid weight) reported in an embryotoxicity study with American kestrels (Falco sparverius). As a surrogate for Forster’s terns, common tern (Sterna hirundo) eggs were treated by air cell injection with corn oil vehicle (control) or a commercial penta-BDE formulation (DE-71) at nominal concentrations of 0.2, 2, and 20 μg g⁻¹ egg. As a positive control, kestrel eggs received vehicle or 20 μg DE-71 g⁻¹ egg. In terns, there were no effects of DE-71 on embryonic survival, and pipping or hatching success; however, treated eggs hatched later (0.44 d) than controls. Organ weights, organ-to-body weight ratios, and bone lengths did not differ, and histopathological observations were unremarkable. Several measures of hepatic oxidative stress in hatchling terns were not affected by DE-71, although there was some evidence of oxidative DNA damage (8-hydroxy-deoxyguanosine; 8-OH-dG). Although DE-71 did not impair pipping and hatching of kestrels, it did result in a delay in hatch, shorter humerus length, and reduced total thyroid weight. Concentrations of oxidized glutathione, reduced glutathione, thiobarbituric acid reactive substances, and 8-OH-dG in liver were greater in DE-71-treated kestrels compared to controls. Our findings suggest common tern embryos, and perhaps other tern species, are less sensitive to PBDEs than kestrel embryos.