Effects of crude oil on water and tracer movement in the unsaturated and saturated zones.

A tracer test was conducted to aid in the investigation of water movement and solute transport at a crude-oil spill site near Bemidji, Minnesota. Time of travel was measured using breakthrough curves for rhodamine WT and bromide tracers moving from the soil surface through oil-contaminated and oil-free unsaturated zones to the saturated zone. Results indicate that the rates of tracer movement were similar in the oil-free unsaturated and saturated zones compared to the oily zones. These results are somewhat surprising given the oil contamination in the unsaturated and saturated zones. Rhodamine tracer breakthrough in the unsaturated and saturated zones in general was delayed in comparison to bromide tracer breakthrough. Peak tracer concentrations for the lysimeters and wells in the oily zone were much greater than at the corresponding depths in the oil-free zone. Water and tracer movement in the oily zone was complicated by soil hydrophobicity and decreased oil saturations toward the periphery of the oil. Preferential flow resulted in reduced tracer interaction with the soil, adsorption, and dispersion and faster tracer movement in the oily zone than expected. Tracers were freely transported through the oily zone to the water table. Recharge calculations support the idea that the oil does not substantially affect recharge in the oily zone. This is an important result indicating that previous model-based assumptions of decreased recharge beneath the oil were incorrect. Results have important implications for modeling the fate and transport of dissolved contaminants at hydrocarbon spill sites.

Leaching of the Neonicotinoids Thiamethoxam and Imidacloprid from Sugar Beet Seed Dressings to Subsurface Tile Drains.

Pesticide transport from seed dressings toward subsurface tile drains is still poorly understood. We monitored the neonicotinoid insecticides imidacloprid and thiamethoxam from sugar beet seed dressings in flow-proportional drainage water samples, together with spray applications of bromide and the herbicide S-metolachlor in spring and the fungicides epoxiconazole and kresoxim-methyl in summer. Event-driven, high first concentration maxima up to 2830 and 1290 ng/L for thiamethoxam and imidacloprid, respectively, were followed by an extended period of tailing and suggested preferential flow. Nevertheless, mass recoveries declined in agreement with the degradation and sorption properties collated in the groundwater ubiquity score, following the order bromide (4.9%), thiamethoxam (1.2%), imidacloprid (0.48%), kresoxim-methyl acid (0.17%), S-metolachlor (0.032%), epoxiconazole (0.013%), and kresoxim-methyl (0.003%), and indicated increased leaching from seed dressings compared to spray applications. Measured concentrations and mass recoveries indicate that subsurface tile drains contribute to surface water contamination with neonicotinoids from seed dressings.

Preparation of alumina nanoshell coated porous silica spheres for inorganic anions separation.

It had been reported that alumina nanoshell coating could be obtained on the external surface of various substrates in one-nanometer precision in aqueous solution. In this work, alumina nanoshell coated mesoporous silica microbeads (nanoAl2O3/mesoSiO2) were prepared with the similar method, and were successfully applied to inorganic anions separation. As the mass transfer speed is largely constrained in the mesopore compared with that on the open surface, it was found that a complete alumina nanoshell coating could be obtained within the mesopore until the five-time coating was carried out. After characterization by BET, SEM and FTIR, it was found that the obtained nanoAl2O3/mesoSiO2 particles are smooth and well dispersed, and the mesopores are well reserved. In addition, the full coverage of nanoAl2O3 shell in mesopores was also confirmed by the binding capacity experiments with berberine. Finally, the nanoAl2O3/mesoSiO2 particles were packed in silica capillary for the separation of inorganic anions I(-), SCN(-), Br(-), NO2(-) and NO3(-) with ion chromatography (IC), and a column efficiency of 3.8 × 10(4) plates per meter was obtained for I(-).

Iodide, bromide, and ammonium in hydraulic fracturing and oil and gas wastewaters: environmental implications.

The expansion of unconventional shale gas and hydraulic fracturing has increased the volume of the oil and gas wastewater (OGW) generated in the U.S. Here we demonstrate that OGW from Marcellus and Fayetteville hydraulic fracturing flowback fluids and Appalachian conventional produced waters is characterized by high chloride, bromide, iodide (up to 56 mg/L), and ammonium (up to 420 mg/L). Br/Cl ratios were consistent for all Appalachian brines, which reflect an origin from a common parent brine, while the I/Cl and NH4/Cl ratios varied among brines from different geological formations, reflecting geogenic processes. There were no differences in halides and ammonium concentrations between OGW originating from hydraulic fracturing and conventional oil and gas operations. Analysis of discharged effluents from three brine treatment sites in Pennsylvania and a spill site in West Virginia show elevated levels of halides (iodide up to 28 mg/L) and ammonium (12 to 106 mg/L) that mimic the composition of OGW and mix conservatively in downstream surface waters. Bromide, iodide, and ammonium in surface waters can impact stream ecosystems and promote the formation of toxic brominated-, iodinated-, and nitrogen disinfection byproducts during chlorination at downstream drinking water treatment plants. Our findings indicate that discharge and accidental spills of OGW to waterways pose risks to both human health and the environment.

The occurrence of bromide in herbal drugs: is there a need for a Ph. Eur. limit?

This contribution provides an overview on the current legal requirements regarding limits for bromide and presents data on the actual bromide burden of commonly used herbal drugs. Evaluation of an extensive data base shows that results exceeding the limit of 50 mg/kg are found in specific plants which take up bromide to a high extent from the environment. Thus, positive findings of bromide in herbal drugs do not necessarily serve as a proof for methyl bromide treatment. Taking into account the ADI recommended by EMA and WHO, there are no toxicological concerns with regard to the intake of herbal teas, extracts or comminuted herbal drugs at therapeutic doses. Furthermore, the use of methyl bromide and other fumigants must be documented within the batch documentation. If stated in the batch documentation that no fumigation was carried out, it is not necessary to perform the test on bromide. In cases of a particular suspect and if toxicological concerns exist, additional testing can be performed in accordance with the limits set by Regulation (EC) No. 396/2005. For the above reasons, information obtained by performing the test on bromide is not significant for the assessment of quality. Therefore, it seems no longer necessary to maintain bromide in Ph. Eur. general chapter 2.8.13. Pesticide residues and it is recommended to delete it from Table 2.8.13.-1.

Measurement and computation of movement of bromide ions and carbofuran in ridged humic-sandy soil.

Water flow and pesticide transport in the soil of fields with ridges and furrows may be more complex than in the soil of more level fields. Prior to crop emergence, the tracer bromide ion and the insecticide carbofuran were sprayed on the humic-sandy soil of a potato field with ridges and furrows. Rainfall was supplemented by sprinkler irrigation. The distribution of the substances in the soil profile of the ridges and furrows was measured on three dates in the potato growing season. Separate ridge and furrow systems were simulated by using the pesticide emission assessment at regional and local scales (PEARL) model for pesticide behavior in soil-plant systems. The substances travelled deeper in the furrow soil than in the ridge soil, because of runoff from the ridges to the furrows. At 19 days after application, the peak of the bromide distribution was measured to be in the 0.1-0.2 m layer of the ridges, while it was in the 0.3-0.5 m layer of the furrows. After 65 days, the peak of the carbofuran distribution in the ridge soil was still in the 0.1 m top layer, while the pesticide was rather evenly distributed in the top 0.6 m of the furrow soil. The wide ranges in concentration measured with depth showed that preferential water flow and substance transport occurred in the sandy soil. Part of the bromide ion distribution was measured to move faster in soil than the computed wave. The runoff of water and pesticide from the ridges to the furrows, and the thinner root zone in the furrows, are expected to increase the risk of leaching to groundwater in ridged fields, in comparison with more level fields.

Metals, non-metals and PCB in electrical and electronic waste--actual levels in Switzerland.

The chemical composition of waste of small electrical and electronic equipment (s-WEEE), a rapidly growing waste stream, was determined for selected metals (Cu, Sb, Hg etc.) and non-metals (Cl, Br, P) and PCBs. During a 3-day experiment, all output products and the s-WEEE input mass flows in a WEEE recycling plant were measured. Only output products were sampled and analyzed. Material balances were established, applying substance flow analysis (SFA). Transfer coefficients for the selected substances were also determined. The results demonstrate the capability of SFA to determine the composition of the highly heterogeneous WEEE for most substances with rather low uncertainty (2 sigma +/- 30%). The results confirm the growing importance of s-WEEE regarding secondary resource metals and potential toxic substances. Nowadays, the thirty times smaller s-WEEE turns over larger flows for many substances, compared to municipal solid waste. Transfer coefficient results serve to evaluate the separation efficiency of the recycling process and confirm--with the exception of PCB and Hg--the limitation of hand-sorting and mechanical processing to separate pollutants (Cd, Pb, etc.) out of reusable fractions. Regularly applied SFA would serve to assess the efficacy of legislative, organizational and technical measures on the WEEE.

[Correlation of mercury, selenium and other elements in the tissues of fishes from the regions at different mercury exposure level].

The contents of selenium and other elements in fish liver and muscle tissues collected from mercury polluted area of Wanshan, Guizhou province of China and non-known mercury polluted one of Beijing were determined with instrumental neutron activation analysis, and that of mercury was determined with atomic fluorescence spectrometry. The correlation among the determined elements, especially between mercury and selenium, in the fish tissues were studied. For most of the elements significant difference of elemental content was found between tissues of liver and muscle, and mostly the content in liver was higher than that in muscle. It was interesting to note that the average content of mercury in Guizhou fish liver was 25-fold higher than that in Beijing one, and 5-fold higher in Guizhou fish muscle than that in Beijing one. For most of the elements no significant difference on the average content was found between the same tissues of the two areas. The molar ratio of Hg/Se increased with the increasing of Hg content at the low Hg level, but the alteration trend became gently and reached to a higher constant value (about 0.2) at the higher Hg level. Only the element of bromine and rubidium was found to have strong linear correlation between the two different tissues of liver and muscle. Though certain correlation existed among the different elements of fish tissues from the two areas, the most significant and the closest one existed between the mercury and selenium of muscle tissue of Guizhou fishes. A closer correlation was also found between them of liver tissue of Guizhou fishes. As for Beijing fish tissues, the correlation of mercury and selenium only existed in liver but no correlation of them was found in muscle. Our results confirm the fact that a certain interaction exists between mercury and selenium in organisms including fish, and it is more evident as the mercury-exposed level is higher. Some significant correlation was also observed between other elements, such as potassium and sodium, cesium and rubidium, iron and zinc, in fish tissues and it could be well explained by their similar chemical and physical properties or their different biological functions.

Solute transport modeling under cultivated sandy soils and transient water regime.

Drainable lysimeters offer the possibility to integrate heterogeneous solute leaching conditions caused by row crops and transient water regime, and to conveniently measure water and solute fluxes at the drainage outlet. To compare solute leaching behavior in and around drainable lysimeters operating under a transient water regime in potato (Solanum tuberosum L.) fields, parameters of the convective lognormal transfer (CLT) function model were fitted using bromide (Br-) flux concentrations (Cf) measured in lysimeters and from Br- resident concentrations (Cr) measured in adjacent soil cores. Expected mean values Ez(I) obtained from Cr and Cf CLT parameters were equivalent and well correlated (R2 = 0.78). However, estimated median values mu of the CLT function were smaller when derived from Cr (1.05 to 1.28) compared with Cf (1.23 to 2.14). Most mu values were also smaller than previously reported values for a 30-cm reference depth, indicating that 50% of solute mass would leach more readily in these coarse sandy soils. Higher variance and dispersion of Cr compared with those of Cf could be related to a smaller sampling support (sample size/sampling area) in the case of Cr measured by soil coring, or to disruption of solute transport mechanisms in the repacked lysimeter. Retained Br- in the top soil layer after 12 to 17 cm of cumulative drainage was indicated by measured Cr. Neither CLT function simulated well residual topsoil Cr values, indicating that Br- plant cycling or preferential flow probably interfered even though tuber Br- uptake was relatively small.

Poisoning from a dietary supplement administered during hospitalization.

Increasing numbers of persons use dietary supplements (DS). Patients who believe in the effectiveness of DS may continue to take them on admission to a health care facility. We present the case of a child who received a DS on a daily basis as an outpatient, continued its use after admission to the hospital, and became poisoned by it during his hospitalization.

Oil production, agriculture, and groundwater quality in the southeastern Gulf Coast Aquifer, Texas.

Associations between groundwater quality and land use were evaluated in the southeastern Gulf Coast Aquifer, Texas. Data from 19234 oil/gas wells and 256 water wells were mapped with a geographic information system (GIS) and statistically analyzed. Water wells near oil/gas wells had significantly higher levels of chloride, bromide, and total dissolved solids (TDS). Bromide-chloride ratios were also higher at water wells near oil/gas wells. Shallower water wells had significantly higher chloride, bromide, TDS, and nitrate concentrations. Nitrate concentrations were higher beneath cropland compared to other land uses. Results of this study suggest that oil/gas production and agriculture have impacted water quality in the Gulf Coast Aquifer.

Effects of brine injection wells, dry holes, and plugged oil/gas wells on chloride, bromide, and barium concentrations in the Gulf Coast Aquifer, southeast Texas, USA.

Data from 1,122 brine injection wells, 24,515 dry holes, 20,877 plugged oil/gas wells, and 256 water wells were mapped with a geographic information system (GIS) and statistically analyzed. There were 9, 107, and 58 water wells within 750 m of a brine injection well, dry hole, or plugged oil/gas well, respectively. Computed median concentrations were 157 mg/l for chloride, 0.8 mg/l for bromide, and 169 microg/l for barium. The maximum chloride concentration was 2,384 mg/l, close to 10 times the secondary drinking water standard. Shallow water wells and water wells near plugged oil/gas wells had significantly higher chloride and bromide levels.

Practical applications of element-specific detection by inductively coupled plasma atomic emission spectroscopy and inductively coupled plasma mass spectrometry to ion chromatography of foods.

Three practical examples are presented to demonstrate the utility of element-selective detection for ion chromatography (IC). The determination of As species in a liquid health food supplement by IC with inductively coupled plasma atomic emission spectroscopy (IC-ICP-AES) is shown to confirm results obtained for total As. IC-ICP-AES is also used to investigate the identity of an unknown peak in a sample of shrimp commercially treated with tripolyphosphate. Finally, results are presented for the determination of residual bromate in baked goods by IC with inductively coupled plasma mass spectrometry detection.

Pesticide residues in black tea.

An investigation of residues of organochlorine and organophosphorous pesticides, as well as of a number of fungicides and of inorganic bromide in 99 samples of black tea taken on the Danish market is reported. The type of pesticide residues involved appear to be very uniform within each country of origin, whereas there are distinct differences between individual countries. Tea from Sri Lanka seems to contain less and fewer residues than tea from the other big tea producing countries. A great many of the samples contained alpha-HCH, lindane and DDT. The use of alpha-HCH and DDT is prohibited in Denmark. Only few other pesticides were detected and at a much lower frequency. None of the teas contained residues that may be regarded as being injurious to health.

[Benz(a)pyrene content in the salt samples obtained from the borehole waters of the Krasnodar deposit]. / O soderzhanii benz(a)pirena v obraztsakh soli, poluchaemoi iz burivykh vod Krasnodarskogo mestorozhdeniia.

Benz(a)pyrene content in the samples of salt obtained from water ground of the Krasnodar field was assayed by means of the spectral fluorescent method. The table salt "Extra" manufactured by the Slavyansk salt-works supplying the trade network (GOST 13830-68) served as control. 15 samples (60 reference standards) were examined. It was established that 3 of 5 tested samples obtained from purified concentrated brine of water ground of the Krasnodar field contained benz(a)pyrene in an amount of 0.0351 microgram/kg up to 0.16 microgram/kg. Benz(a)pyrene (0.104 microgram/kg) was detected in 1 of 4 tested samples of the salt "Extra". It is concluded that tested salt samples obtained from concentrated brine of water ground of the Krasnodar field contain an insignificant amount of benz(a)pyrene.