Precipitation Amount and Intensity Trends Across Southwest Saudi Arabia

This study examines precipitation accumulation and intensity trends across a region in southwest Saudi Arabia characterized by distinct seasonal weather patterns and mountainous terrain. The region is an example of an arid/semiarid area faced with maintaining sustainable water resources with a growing population. Annual and seasonal trends in precipitation amount were examined from 29 rain gages divided among four geographically unique regions from 1945/1946 to 2009. Two of the regions displayed significantly declining annual trends over the time series using a Mann‐Kendall test modified for autocorrelation (α < 0.05). Seasonal analysis revealed insignificant declining trends in at least two of the regions during each season. The largest and most consistent declining trends occurred during wintertime where all regions experienced negative trends. Several intensity metrics were examined in the study area from four additional stations containing daily data from 1985 to 2011. Intensity metrics included total precipitation, wet day count, simple intensity index, maximum daily annual rainfall, and upper/lower precipitation distribution changes. In general, no coherent trends were found among the daily stations suggesting precipitation is intensifying across the study area. The work represents the first of its size in the study area, and one of few in the region due to the lack of available long‐term data needed to properly examine precipitation changes.     

Dissipation of Contaminants of Emerging Concern in Biosolids Applied to Nonirrigated Farmland in Eastern Colorado

In 2007, a 1.5‐year field‐scale study was initiated by the U.S. Geological Survey to evaluate the dissipation of contaminants of emerging concern (CECs) following a first agronomic biosolids application to nonirrigated farmland. CECs with the greatest decrease in concentration in the surface biosolids at 180 days post‐application included indole, d‐limonene, p‐cresol, phenol, and skatol. CECs that were present in the largest concentration in 180‐day‐weathered biosolids included stanols, nonylphenols, bisphenol A, bis(2‐ethylhexyl) phthalate, hexahydrohexamethyl cyclopenta‐benzopyran (HHCB), and triclosan. CECs that were detected in pre‐application soil were 3‐beta coprostanol, skatol, acetophenone, beta‐sitosterol, beta‐stigmastanol, cholesterol, indole, p‐cresol, and phenol, most of which are biogenic sterols or fragrances that have natural plant sources in addition to anthropogenic sources, yet their concentrations increased (in some cases, substantially) following biosolids application. Preliminary data indicate the nonylphenols (including NPEO1, NPEO2), OPEO1, benzo[a]pyrene, diethyl phthalate, d‐limonene, HHCB, triclosan, and possibly 3‐beta coprostanol, skatol, beta‐sitosterol, cholesterol, indole, and p‐cresol, migrated downward through the soil by 468 days post‐application, but indicated little uptake by mature wheat plants. This study indicates that some CECs are sufficiently persistent and mobile to be vertically transported into the soil column following biosolids applications to the land surface, even in semiarid regions.     

Kinetic modeling of bioavailability for sorbed-phase 2,4-dichlorophenoxyacetic acid

The degradation rate of 2,4-dichlorophenoxyacetic acid (2,4-D) was studied in silica-slurry systems to evaluate the bioavailability of sorbed-phase contaminant. After the silica particles were saturated with 2,4-D, the system was inoculated with the 2,4-D-degrading microorganism Flavorbacterium sp. strain FB4. The disappearance rate of 2,4-D was found to be greater than the rate predicted based upon liquid-phase 2,4-D concentrations. A kinetic formulation, termed the enhanced bioavailability model, was developed to describe the desorption and biodegradation processes in this batch system. The approach assumes that 2,4-D resides in both the liquid and solid phases and degradation occurs via both suspended and attached biomass. All biomass can degrade liquid-phase 2,4-D at one rate, while only attached biomass can degrade sorbed 2,4-D at another rate. An enhanced transformation factor (Ef) was introduced to express the increased biodegradation rate over that expected from the liquid phase only. This approach was able to account for the increased degradation rates observed experimentally. The results provide evidence that desorption to the bulk solution is not prerequisite to degradation, and that sorbed substrate may be available for degradation.     

Uptake of gamma-HCH (Lindane) by pipistrelle bats and its effect on survival

Adult pipistrelle bats were caught at two roosts in Eastern England and kept in captivity on an ad lib diet of mealworms. In Experiment 1, two groups of eight bats were each kept in identical outdoor enclosures where the bats could fly freely and where they had a choice of five roost boxes, one of which was heated. One of these groups was exposed to gamma-HCH applied to planed pine blocks which had been immersed in a hexane solution of gamma-HCH. An initial concentration, estimated from surface wood scrapings, of 9.94 +/- 1.15 mg m(-2) was used for the first 44 days, while 866 +/- 51 mg g(-2) was used for a further 44 days. Blocks were placed in the roost boxes to simulate the type of exposure experienced by wild bats. Blocks dosed with solvent alone were given to the other group of bats (controls). Six of the eight bats in the group exposed to gamma-HCH died, while all bats in the control group survived (P < 0.007). In Experiment 2, three groups of five bats were kept in identical cages. Two groups were exposed to identical wood blocks dosed with gamma-HCH, which gave a concentration of 211 mg m(-2) in surface scrapings taken 1-2 h after dosing, while the other group received a wood block treated with solvent alone (control). All bats in the groups exposed to gamma-HCH died within 17 days, while all bats in the control group survived (P < 0.001). Tissues of bats were analysed for gamma-HCH by gas chromatography. There was a critical concentration of 622 +/- 102 microg gamma-HCH g(-1) extractable lipid at which bats died. The total weight of gamma-HCH in bat carcasses was directly related to the weight of extractable lipid. On average, bats died when the gamma-HCH concentration in the whole body reached 27.9 +/- 4.8 microg g(-1), but this value increased as body weight increased. This study confirmed the results of a previous study that gamma-HCH is toxic to bats in conditions simulating exposure in the wild.     

Nutrient limitation in soils exhibiting differing nitrogen availabilities: what lies beyond nitrogen saturation?

The nature of nutrient limitation in large areas of temperate forest may be changing due to human activities. As N availability in these forests increases, other nutrients could increasingly constrain productivity and other ecosystem processes. To determine the nature of nutrient limitation (N, P, and Ca) in forest soils exhibiting differing N availability, we conducted three field studies in the Fernow Experimental Forest, West Virginia, USA. The first used a ubiquitous herbaceous species, Viola rotundifolia, to compare indices of N availability to the activity of root-associated phosphomonoesterase (PME) activity at two spatial scales. The second study used fertilized, root in-growth cores to assess the extent of N, P, and Ca limitation. Finally, we measured the root-associated PME activity of V. rotundifolia growing in experimental plots that have received various combinations of nutrient additions and harvest treatments. For entire watersheds, stream water nitrate concentrations were positively related to PME activities (R2 = 0.986). For small plots, PME activities were positively associated with soil nitrate availability (R2 = 0.425), and to a lesser extent with the leaf N concentrations (R2 = 0.291). Root growth into microsites fertilized with P was greater than growth into microsites fertilized with either N or Ca, especially in watersheds with high N availability. Experimental additions of N increased the root-associated PME activity of V. rotundifolia, supporting the causality of the relationship between N availability and PME activity. Collectively, our results indicate that, as N availability increases, P becomes increasingly limiting at the sites examined. Understanding how nutrient limitations change during N saturation should improve ecosystem models and better inform our attempts to mitigate any undesired effects.     

Spatial and temporal occurrence of N-nitrosamines in seven drinking water supply systems

The spatiotemporal presence of eight N-nitrosamines in the water of seven supply systems in Quebec considered to be susceptible to these emerging disinfection by-products was evaluated. This is the first study on the presence of N-nitrosamines in drinking water utilities in Quebec. Seven sampling campaigns were carried out at several sampling points in each of the systems over a period of 1 year. The results show that N-nitrosamines, primarily N-nitrosodimethylamine (NDMA), were not commonly detected in the water of the facilities under study (10 % of samples). The concentrations measured were lower than those reported in recent North American studies. None of the 195 samples taken exceeded the Ontario standard of 9 ng/L for NDMA (maximum value observed of 3.3 ng/L). N-nitrosomethylethylamine and N-nitrosopiperidine were detected once, with concentrations of 3.7 and 6.0 ng/L, respectively. Chloramination was identified as being the main risk factor regarding the presence of N-nitrosamines, but water quality and some operating parameters, in particular disinfectant residual, also seem to be related to their presence. NDMA concentrations at the end of the distribution systems were generally higher than water leaving the plant. No seasonal trends were observed for the formation of N-nitrosamines in the investigated supply systems. Finally, an association between the presence of N-nitrosamines and the levels of trihalomethanes and haloacetic acids was observed in some facilities.     

Geospatial approaches to characterizing agriculture in the Chincoteague Bay Subbasin

Most agricultural information is reported by government sources on a state or county basis. The purpose of this study was to demonstrate use of geospatial data, the 2002 Agricultural Cropland Data Layer (CDL) for the mid-Atlantic region, to characterize agricultural, environmental, and other scientific parameters for the Chincoteague Bay subbasin using geographic information systems. This study demonstrated that agriculture can be characterized accurately on subbasin and subwatershed bases, thus complimenting various assessment technologies. Approximately 28% of the dry land of the subbasin was cropland. Field corn was the largest crop. Soybeans, either singly or double-cropped with wheat, were the second most predominant crop. Although the subbasin is relatively small, cropping practices in the northern part were different from those in the southern portion. Other crops, such as fresh vegetables and vegetables grown for processing, were less than 10% of the total cropland. A conservative approximation of the total pesticide usage in the subbasin in 2002 was over 277,000 lbs of active ingredients. Herbicides represented the most frequently used pesticides in the subbasin, both in number (17) and in total active ingredients (over 261,000 lbs). Ten insecticides predominated in the watershed, while only small quantities of three fungicides were used. Total pesticide usage and intensity were estimated using the CDL. Nutrient inputs to cropland from animal manure, chemical fertilizer, and atmospheric deposition were modeled at over 30 million pounds of nitrogen and over 7 million pounds of phosphorous. Crops under conservation tillage had the largest input of both nutrients.     

Validation of reliable and selective methods for direct determination of glyphosate and aminomethylphosphonic acid in milk and urine using LC-MS/MS

Simple high-throughput procedures were developed for the direct analysis of glyphosate [N-(phosphonomethyl)glycine] and aminomethylphosphonic acid (AMPA) in human and bovine milk and human urine matrices. Samples were extracted with an acidified aqueous solution on a high-speed shaker. Stable isotope labeled internal standards were added with the extraction solvent to ensure accurate tracking and quantitation. An additional cleanup procedure using partitioning with methylene chloride was required for milk matrices to minimize the presence of matrix components that can impact the longevity of the analytical column. Both analytes were analyzed directly, without derivatization, by liquid chromatography tandem mass spectrometry using two separate precursor-to-product transitions that ensure and confirm the accuracy of the measured results. Method performance was evaluated during validation through a series of assessments that included linearity, accuracy, precision, selectivity, ionization effects and carryover. Limits of quantitation (LOQ) were determined to be 0.1 and 10 µg/L (ppb) for urine and milk, respectively, for both glyphosate and AMPA. Mean recoveries for all matrices were within 89–107% at three separate fortification levels including the LOQ. Precision for replicates was ≤7.4% relative standard deviation (RSD) for milk and ≤11.4% RSD for urine across all fortification levels. All human and bovine milk samples used for selectivity and ionization effects assessments were free of any detectable levels of glyphosate and AMPA. Some of the human urine samples contained trace levels of glyphosate and AMPA, which were background subtracted for accuracy assessments. Ionization effects testing showed no significant biases from the matrix. A successful independent external validation was conducted using the more complicated milk matrices to demonstrate method transferability.