Accumulation of 14C-trinitrotoluene and related nonextractable (bound) residues in Eisenia fetida

To determine if trinitrotoluene (TNT) forms nonextractable residues in earthworms and to measure the relative degree of accumulation as compared to TNT and its deaminated metabolites, Eisenia fetida was exposed to ¹⁴C-TNT using dermal contact to filter paper or exposure to soil. Nonextractable residues made up 32-68% of total body burden depending on exposure media and depuration time. Parent TNT accounted for less than 3% of radioactivity, while ADNTs accounted for 7-38%. Elimination half-lives were 61-120 h for TNT, ADNTs, and DANTs, which was significantly lower than the half-lives found for nonextractable residues, 201-240 h. However, over 80% of the nonextractable residue was solubilized using weak acid (pH 2). Based on our findings that TNT accumulation occurs primarily as nonextractable residues, which have a longer half-life, and that nonextractable residues can be solubilized, we propose that nonextractable residues could be used as a selective biomarker for assessing TNT contamination.     

Full‐scale bioremediation of a dilute 50‐acre plume

Enhanced anaerobic dechlorination is being conducted to remediate a 50‐acre groundwater area impacted with chlorinated volatile organic compounds (CVOCs). The plume, which is over 3,000 feet (ft) long, initially contained tetrachloroethene and breakdown products at concentrations of 2 to 3 milligrams per liter. The site's high groundwater flow velocity (greater than 1,000 ft per year) was incorporated into the design to help with amendment distribution. Bioaugmentation was conducted using a mixed culture containing Dehalococcoides ethenogenes. There is evidence that it has migrated to distances exceeding 600 ft. The major benefit of the high groundwater flow velocity is greater areal coverage by the remediation system, but the downside is the difficulty in delivering sufficient donor to create the required anaerobic conditions. Overall performance has been excellent with total CVOC reductions and conversion to ethene of 98 percent within a 25‐acre area downgradient of the treatment transect that has operated the longest. © 2011 Wiley Periodicals, Inc.     

Instream sensor results suggest soil–plant processes produce three distinct seasonal patterns of nitrate concentrations in the Ohio River Basin

The Ohio River Basin (ORB) is responsible for 35% of total nitrate loading to the Gulf of Mexico yet controls on nitrate timing require investigation. We used a set of submersible ultraviolet nitrate analyzers located at 13 stations across the ORB to examine nitrate loading and seasonality. Observed nitrate concentrations ranged from 0.3 to 2.8 mg L⁻¹ N in the Ohio River's mainstem. The Ohio River experiences a greater than fivefold increase in annual nitrate load from the upper basin to the river's junction with the Mississippi River (74–415 Gg year⁻¹). The nitrate load increase corresponds with the greater drainage area, a 50% increase in average annual nitrate concentration, and a shift in land cover across the drainage area from 5% cropland in the upper basin to 19% cropland at the Ohio River's junction with the Mississippi River. Time-series decomposition of nitrate concentration and nitrate load showed peaks centered in January and June for 85% of subbasin-year combinations and nitrate lows in summer and fall. Seasonal patterns of the terrestrial system, including winter dormancy, spring planting, and summer and fall growing-harvest seasons, are suggested to control nitrate timing in the Ohio River as opposed to controls by river discharge and internal cycling. The dormant season from December to March carries 51% of the ORB's nitrate load, and nitrate delivery is high across all subbasins analyzed, regardless of land cover. This season is characterized by soil nitrate leaching likely from mineralization of soil organic matter and release of legacy nitrogen. Nitrate experiences fast transit to the river owing to the ORB's mature karst geology in the south and tile drainage in the northwest. The planting season from April to June carries 26% of the ORB's nitrate and is a period of fertilizer delivery from upland corn and soybean agriculture to streams. The harvest season from July to November carries 22% of the ORB's nitrate and is a time of nitrate retention on the landscape. We discuss nutrient management in the ORB including fertilizer efficiency, cover crops, and nitrate retention using constructed measures.     

Passenger head kinematics in abrupt braking and lane change events

Abstract

Objective: A test track study was conducted to quantify patterns of adult front seat passenger head motion during abrupt vehicle maneuvers.

Method: Eighty-seven men and women with a wide range of body sizes and ages participated in data collection on a closed test track in a passenger sedan under manual control by a test driver. Because a primary goal of the study was to gather “unaware” data, the participants were instructed that the study was concerned with vehicle dynamics and they were required to read from a questionnaire taped to the top of their thighs as the drive began. The first event was a hard brake (approximately 1 g) to a stop from 35?mph (56 kph). Within the space of approximately 5?min the participants also experienced an aggressive lane change, a sharp right turn with simultaneous hard braking, and a second hard braking event. A Microsoft Kinect v2 sensor was positioned to view the area around the front passenger seat. Head location was tracked using the Kinect data with a novel methodology that fit 3D head scan data to the depth data acquired in the vehicle.

Result: The mean (standard deviation) forward excursion of the estimated head center of gravity (CG) location in the first braking event was 135 (62) mm. The forward head CG excursion in the second braking event of 115 (51) mm was significantly less than that in the first, but the difference was small relative to the within-condition variance. Head excursion on the second braking trial was less than that on the first trial for 69% of participants. The mean maximum inboard head excursion in lane-change maneuvers was 118 (40) mm. Forward head excursions in braking were significantly smaller for older passengers and those with higher body mass index, but the combined factors accounted for less than 25% of the variance. Inboard head excursion in the lane-change event was significantly related to stature, but only about 7% of variance was related to body size. Head excursions for men and women did not differ significantly after accounting for body size.

Discussion: This is the first quantitative occupant dynamics study to use a large, diverse sample of passengers, enabling the exploration of the effects of covariates such as age and body size.

Conclusions: The data demonstrate that a relatively large range of head positions can be expected to result from abrupt vehicle maneuvers. The data do not support simple scaling of excursions based on body size.     

Impact of proposed changes in IESTI equations for short-term dietary exposure to pesticides from Australian and Codex perspective

ABSTRACT

In 2015 a scientific workshop was held in Geneva, where updating the four equations for estimating the short-term dietary exposure (International Estimated Short Term Intake, IESTI) to pesticides was suggested. The impact of these proposed changes on the exposure was studied by using residue data and large portion consumption data from Codex and Australia. For the Codex data, the exposure increased by a median factor of 2.5 per commodity when changing to the proposed IESTI equations. The increase in exposure was highest for bulked and blended food commodities (case 3 equations), followed by medium-sized food commodities (case 2a equations) and small- and large-sized food commodities (case 1 and case 2b equations). For the Australian data, out of 184 maximum residue limit (MRL) large portion combinations showing acute exposures below the acute reference dose (ARfD) with the current IESTI equations, 23 exceeded the ARfD with the proposed IESTI equations (12%). The percentage exceeding the ARfD was higher for the Australian MRL large portion combinations (12% of 184) than for those of Codex (1.3% of 8,366). However, the percentage MRL loss in the Australian dataset may not be representative of all pesticide MRLs since it concerns six pesticides only, specifically selected to elucidate the potential effects of the use of the proposed IESTI equations. For the Codex data, the increase in exposure using the proposed equations resulted in a small increased loss of 2.6% of the 1,110 MRLs estimated by the Joint FAO/WHO Meeting on Pesticide Residues (JMPR): 1.4% of the MRLs were already not acceptable with the current equations, 4.0% of the MRLs were not acceptable with the newly proposed equations. Our study revealed that case 3 commodities may be impacted more by the proposed changes than other commodities. This substantiates one of the conclusions of the Geneva workshop to gather information on bulking and blending practices in order to refine MRL setting and dietary risk assessment for case 3 commodities where possible.     

Regional assessment of herbicide sorption and degradation in two sampling years

Sorption and degradation of the herbicide 2,4-D [2,4-dichlorophenoxyacetic acid] were determined for 123 surface soils (0 to 15 cm) collected in 2002 and in 2004 between 49 degrees to 60 degrees north longitude and 110 degrees to 120 degrees west latitude in Alberta, Canada. The soils were characterized by soil organic carbon content (SOC), pH, electrical conductivity, soil texture, cation exchange capacity, carbonate content, and total soil microbial activity. The 2,4-D sorption coefficients, Kd and Koc, were highly variable with coefficients of variation of 89 and 59%, respectively, at the provincial scale. Both Kd and Koc were well described by regression models with SOC and soil pH as variables, regardless of scale. Surprisingly, variations in 2,4-D mineralization were much smaller than variations in sorption. Variability in total 2,4-D mineralization was particularly low, with a coefficient of variation of only 7% at the provincial scale. Average 2,4-D half-lives in ecoregions ranged from 1.7 to 3.5 d, much lower than the field dissipation half-life of 10 d reported for 2,4-D in general pesticide property databases. Regression models describing degradation parameters were generally poor or not significant because 2,4-D mineralization was only weakly associated with measured 2,4-D sorption parameters and soil properties. As such, regional variations in herbicide sorption coefficients should be measured or calculated based on soil properties, to assign distinct pesticide fate model input parameters when estimating 2,4-D off-site transport at the provincial scale. Spatial variations in herbicide degradation appear less important for Alberta as 2,4-D half-lives were similar in soils across the province. The rapid mineralization of 2,4-D is noteworthy because 2,4-D is widely used in Alberta and perhaps adaptation of soil microbial communities allowed for accelerated degradation regardless of soil properties or the extent of 2,4-D sorption by soil.     

Atrazine dissipation in s-triazine-adapted and nonadapted soil from Colorado and Mississippi: implications of enhanced degradation on atrazine fate and transport parameters

Soil bacteria have developed novel metabolic abilities resulting in enhanced atrazine degradation. Consequently, there is a need to evaluate the effects of enhanced degradation on parameters used to model atrazine fate and transport. The objectives of this study were (i) to screen Colorado (CO) and Mississippi (MS) atrazine-adapted and non-adapted soil for genes that code for enzymes able to rapidly catabolize atrazine and (ii) to compare atrazine persistence, Q(10), beta, and metabolite profiles between adapted and non-adapted soils. The atzABC and/or trzN genes were detected only in adapted soil. Atrazine's average half-life in adapted soil was 10-fold lower than that of the non-adapted soil and 18-fold lower than the USEPA estimate of 3 to 4 mo. Q(10) was greater in adapted soil. No difference in beta was observed between soils. The accumulation and persistence of mono-N-dealkylated metabolites was lower in adapted soil; conversely, under suboptimal moisture levels in CO adapted soil, hydroxyatrazine concentrations exceeded 30% of the parent compounds' initial mass. Results indicate that (i) enhanced atrazine degradation and atzABC and/or trzN genes are likely widespread across the Western and Southern corn-growing regions of the USA; (ii) persistence of atrazine and its mono-N-dealkylated metabolites is significantly reduced in adapted soil; (iii) hydroxyatrazine can be a major degradation product in adapted soil; and (iv) fate, transport, and risk assessment models that assume historic atrazine degradation pathways and persistence estimates will likely overpredict the compounds' transport potential in adapted soil.     

Pesticides in rain in four agricultural watersheds in the United States

Rainfall samples were collected during the 2003 and 2004 growing seasons at four agricultural locales across the USA in Maryland, Indiana, Nebraska, and California. The samples were analyzed for 21 insecticides, 18 herbicides, three fungicides, and 40 pesticide degradates. Data from all sites combined show that 7 of the 10 most frequently detected pesticides were herbicides, with atrazine (70%) and metolachlor (83%) detected at every site. Dacthal, acetochlor, simazine, alachlor, and pendimethalin were detected in more than 50% of the samples. Chlorpyrifos, carbaryl, and diazinon were the only insecticides among the 10 most frequently detected compounds. Of the remaining pesticide parent compounds, 18 were detected in fewer than 30% of the samples, and 13 were not detected. The most frequently detected degradates were deethylatrazine; the oxygen analogs (OAs) of the organophosphorus insecticides chlorpyrifos, diazinon, and malathion; and 1-napthol (degradate of carbaryl). Deethylatrazine was detected in nearly 70% of the samples collected in Maryland, Indiana, and Nebraska but was detected only once in California. The OAs of chlorpyrifos and diazinon were detected primarily in California. Degradates of the acetanilide herbicides were rarely detected in rain, indicating that they are not formed in the atmosphere or readily volatilized from soils. Herbicides accounted for 91 to 98% of the total pesticide mass deposited by rain except in California, where insecticides accounted for 61% in 2004. The mass of pesticides deposited by rainfall was estimated to be less than 2% of the total applied in these agricultural areas.