AN EVALUATION OF WEEKLY AND MONTHLY TIME SERIES FORECASTS OF MUNICIPAL WATER USE1

ABSTRACT: A cascade model for forecasting municipal water use one week or one month ahead, conditioned on rainfall estimates, is presented and evaluated. The model comprises four components: long term trend, seasonal cycle, autocorrelation and correlation with rainfall. The increased forecast accuracy obtained by the addition of each component is evaluated. The City of Deerfield Beach, Florida, is used as the application example with the calibration period from 1976–1980 and the forecast period the drought year of 1981. Forecast accuracy is measured by the average absolute relative error (AARE, the average absolute value of the difference between actual and forecasted use, divided by the actual use). A benchmark forecast is calculated by assuming that water use for a given week or month in 1981 is the same as the average for the corresponding period from 1976 to 1980. This method produces an AARE of 14.6 percent for one step ahead forecasts of monthly data and 15.8 percent for weekly data. A cascade model using trend, seasonality and autocorrelation produces forecasts with AARE of about 12 percent for both monthly and weekly data while adding a linear relationship of water use and rainfall reduces the AARE to 8 percent in both cases if it is assumed that rainfall is known during the forecast period. Simple rainfall predictions do not increase the forecast accuracy for water use so the major utility of relating water use and rainfall lies in forecasting various possible water use sequences conditioned on sequences of historical rainfall data.     

Evaluating the effects of spatial monitoring policy on groundwater quality portrayal

What size sample is sufficient for spatially sampling ambient groundwater quality? Water quality data are only as spatially accurate as the geographic sampling strategies used to collect them. This research used sequential sampling and regression analysis to evaluate groundwater quality spatial sampling policy changes proposed by California's Department of Water Resources. Iterative or sequential sampling of a hypothetical groundwater basin's water quality produced data sets from sample sizes ranging from 2.8% to 95% coverage of available point sample sites. Contour maps based on these sample data sets were compared to an original (control), mapped hypothetical data set, to determine at which point map information content and pattern portrayal are not improved by increasing sample sizes. Comparing series of contour maps of ground water quality concentration is a common means of evaluating the geographic extent of groundwater quality change. Comparisons included visual inspection of contout maps and statistical tests on digital versions of these map files, including correlation and regression products. This research demonstrated that, down to about 15% sample site coverage, there is no difference between contour maps produced from the different sampling strategies and the contout map of the original data set.     

Structure characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane

1,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) is used primarily as an additive flame retardant. 1H NMR spectroscopy and an X-ray structure determination have revealed that a technical mixture consists largely of two (of the four possible) diastereomers, rac-(1R,2R)-1,2-dibromo-(4S)-4-((1S)-1,2-dibromoethyl)cyclohexane (alpha-TBECH) and rac-(1R,2R)-1,2-dibromo-(4S)-4-((1R)-1,2-dibromoethyl)cyclohexane (beta-TBECH), in a mole ratio of approximately 1:1. The two other possible isomers, gamma- and delta-TBECH, were not detected in a technical mixture. The TBECH isomers are thermally sensitive and can easily interconvert at temperatures of 125 degrees C. A thermal equilibrium mixture of alpha-, beta-, gamma- and delta-TBECH consists of approximately 33%, 33%, 17% and 17% of these isomers, respectively. Separation of all four TBECH diastereomers, with minimal thermal interconversion of the isomers, was achieved by careful selection of GC-capillary column length and injector temperature. Although technical TBECH does not contain the gamma- and delta-isomers, they may still be relevant environmental contaminants since manufacturing processes utilize thermal processes which may induce their formation.     

Structure elucidation of four possible biogenic organohalogens using isotope exchange mass spectrometry

The molecular structures of four unknown bioaccumulating halogenated compounds, C10H6N2Br3Cl3, C10H6N2Br4Cl2, C10H6N2Br5Cl, and C10H6N2Br6 were characterized using isotope exchange positive chemical ionization (IE-PCI) mass spectrometry (MS) and identified by comparison to synthesized standards. NH3 and ND3 were used as reagent gases for the IE-PCI-MS experiment. The shift in mass of the quasimolecular ion between the NH3 and ND3 PCI obtained spectra indicated the number of exchangeable hydrogens attached to the two nitrogen atoms in C10H6N2Br4Cl2, and thus the type of amines present (primary, secondary, or tertiary). 19 compounds (13 amines of varying degree of substitution; six containing no nitrogen) were used as reference compounds and controls in the experiment to validate the IE-PCI technique. The results of the IE-PCI-MS indicated the presence of two tertiary amine functional groups. The molecular structures of the four hexahalogenated compounds were then proposed to be 1,1'-dimethyl-3,3',4,-tribromo-4',5,5'-trichloro-2,2'-bipyrrole, 1,1'-dimethyl-3,3',4,4'-tetrabromo-5,5'-dichloro-2,2'-bipyrrole, 1,1'-dimethyl-3,3',4,4',5-pentabromo-5'-chloro-2,2'-bipyrrole, and 1,1'-dimethyl-3,3',4,4',5,5'-hexabromo-2,2'-bipyrrole and subsequently synthesized. Comparison of retention times and electron capture negative ionization (ECNI) full scans on various gas chromatography (GC) columns between the synthesized bipyrroles and the corresponding unknown compounds in biota indicated that three of the unknown compounds--possible marine natural products--were the proposed halogenated dimethyl bipyrroles. The placement of the halogen atoms on the fourth compound, C10H6N2Br3Cl3 could not be unequivocally determined since the synthesized standard could not be fully characterized.     

Influence of solid dairy manure and compost with and without alum on survival of indicator bacteria in soil and on potato

We measured Escherichia coli, Enterococcus spp. and fecal coliform numbers in soil and on fresh potato skins after addition of solid dairy manure and dairy compost with and without alum (Al(2)(SO(4))(3)) treatment 1, 7, 14, 28, 179 and 297 days after application. The addition of dairy compost or solid dairy manure at rates to meet crop phosphorus uptake did not consistently increase E. coli and Enterococcus spp. and fecal coliform bacteria in the soil. We did not detect E. coli in any soil sample after the first sampling day. Seven, 14, 28, 179 and 297 days after solid dairy waste and compost and alum were applied to soil, alum did not consistently affect Enterococcus spp. and fecal coliform bacteria in the soil. We did not detect E. coli in any soil, fresh potato skin or potato wash-water at 214 days after dairy manure or compost application regardless of alum treatment. Dairy compost or solid dairy manure application to soil at rates to meet crop phosphorus uptake did not consistently increase Enterococcus spp. and fecal coliform numbers in bulk soil. Solid dairy manure application to soil at rates to meet crop phosphorus uptake, increased Enterococcus spp. and fecal coliform numbers in potato rhizosphere soil. However, fresh potato skins had higher Enterococcus spp. and fecal coliform numbers when solid dairy manure was added to soil compared to compost, N and P inorganic fertilizer and N fertilizer treatments. We did not find any E. coli, Enterococcus or total coliform bacteria on the exterior of the tuber, within the peel or within a whole baked potato after microwave cooking for 5 min.     

The sensitivity of modeled ozone to the temporal distribution of point, area, and mobile source emissions in the eastern United States

Ozone remains one of the most recalcitrant air pollution problems in the US. Hourly emissions fields used in air quality models (AQMs) generally show less temporal variability than corresponding measurements from continuous emissions monitors (CEM) and field campaigns would imply. If emissions control scenarios to reduce emissions at peak ozone forming hours are to be assessed with AQMs, the effect of emissions' daily variability on modeled ozone must be understood. We analyzed the effects of altering all anthropogenic emissions' temporal distributions by source group on 2002 summer-long simulations of ozone using the Community Multiscale Air Quality Model (CMAQ) v4.5 and the Carbon Bond IV (CBIV) chemical mechanism with 12 km resolution. We find that when mobile source emissions were made constant over the course of a day, 8-h maximum ozone predictions changed by ±7 parts per billion by volume (ppbv) in many urban areas on days when ozone concentrations greater than 80 ppbv were simulated in the base case. Increasing the temporal variation of point sources resulted in ozone changes of +6 and −6 ppbv, but only for small areas near sources. Changing the daily cycle of mobile source emissions produces substantial changes in simulated ozone, especially in urban areas at night; results suggest that shifting the emissions of NO_x from day to night, for example in electric powered vehicles recharged at night, could have beneficial impacts on air quality.     

Structural characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2,5,6-tetrabromocyclooctane (TBCO)

1,2,5,6-Tetrabromocyclooctane (TBCO) is a commercial brominated flame retardant that is employed mainly as an additive in textiles, paints and plastics. Very little is known about its presence or behavior in the environment or its analysis. TBCO can exist as two diastereomers, the stereochemistries of which have not been previously reported. We have named the first eluting isomer, under HPLC conditions, as alpha-TBCO (α-TBCO) and the later eluting isomer as beta-TBCO (β-TBCO) when using an Acquity UPLC BEH C₁₈ column with methanol/acetonitrile/water as the mobile phase. The structural elucidation of these two isomers was accomplished by ¹H NMR spectroscopy, GC/MS, LC/MS and X-ray structure determinations. α-TBCO is (1R,2R,5S,6S)-1,2,5,6-tetrabromocyclooctane and β-TBCO is rac-(1R,2R,5R,6R)-1,2,5,6-tetrabromocyclooctane. As with some other brominated cycloaliphatic compounds, TBCO is thermally labile and the isomers easily interconvert. A thermal equilibrium mixture of α- and β-TBCO consists of approximately 15% and 85% of these isomers, respectively. Separation of the two diastereomers, with minimal thermal interconversion between them, is achievable by careful selection of GC-capillary column length and injector temperature. LC/MS analyses of TBCO also presents an analytical challenge due to poor resolution of the isomers on chromatographic stationary phases, and weak intensity of molecular ions (or major fragment ions) when using LC-ESI/MS. Only bromide ions were seen in the mass spectra. APCI and APPI also failed to produce the molecular ion with sufficient intensity for identification.     

Vegetated ditches as a management practice in irrigated alfalfa

The organophosphate (OP) insecticides diazinon and chlorpyrifos have been frequently detected in the San Joaquin River, California, USA. Irrigation tail waters are a significant source of OP pesticides in the watershed. This study tested several management practices for reducing offsite movement of chlorpyrifos to surface water from flood irrigated alfalfa. Management practices evaluated include (1) a constructed, vegetated irrigation tailwater return ditch and (2) increased lag time between chlorpyrifos application and start of flood irrigation. Chlorpyrifos concentrations in whole-water samples of irrigation runoff were variable and ranged from 0.22 mug/l to a maximum of 1.67 mug/l. The median concentration reduction at the end of a 200 m vegetated ditch was 38% compared to 1% in an adjacent conventional tail water ditch. Runoff data collected represented first flush runoff from sets that were irrigated between 48 and 144 h after chlorpyrifos application. There was no consistent effect of irrigation lag time on chlorpyrifos concentration in tailwater for lag times of up to 144 h. Consequently these data indicate that delayed irrigation is not an effective management practice for reducing chlorpyrifos off-site movement to surface water in California flood irrigated alfalfa.     

Nitrate levels modulate denitrification activity in tropical mangrove sediments (Goa, India)

A study to examine the short-term effect of nitrate and organic carbon addition on denitrification activity was carried out on sediments from a mangrove ecosystem prone to anthropogenic activities (Divar, Goa, India). Laboratory microcosms were prepared using sediment sectioned at every 2-cm-depth interval from the surface to 10 cm. The incubations were subjected to varying nitrate amendments at concentrations ranging from 0, 5, 10, 20, 40 to 60 ??mol l^???1 (up to three times more than measured in field). Nitrous oxide production rates increased significantly (n?=?15; p?<?0.001) on addition of the nutrient at all depths investigated indicating that denitrification in mangrove sediments was NO $_{3}^{-}$ limited. Incubations amended with organic carbon were prepared using glucose as a substrate with concentrations ranging from 0%, 0.1%, 0.3%, 0.5%, 0.75% to 1%. No significant increase in N₂O production was observed on organic C addition. When both the substrates were in excess (1 mmol KNO₃ + 1 mmol glucose), potential denitrification rates decreased with depth and were up to 38 times higher than the in situ denitrification activity varying from 81.26 to 304.09 ??mol N₂O-N m^???2 h^???1. These results reveal that mangrove sediments could act as a sink for nitrate and microbially mediated denitrification could effectively reduce N load controlling any adverse environmental impact in the adjoining estuarine system.