A Methodological Approach for Exposure Assessment Studies in Residences Using Volatile Organic-Compound-Contaminated Water

Abstract

This paper presents a methodological approach for assessing total exposures to volatile organic compounds (VOCs) in residences using contaminated water supplies. This approach is founded on assessment of ingestion, inhalation, and dermal exposures; both long-term (i.e., 12 to 24 hr) lowlevel exposures and short-term (i.e., =10 min) high-level exposures are considered.

The methodology is based on the collection of water samples to establish the identity of the contaminants, maximum source terms, and possible dermal and ingestion exposures; integrated whole-air samples are collected to assess long- and short-term inhalation exposures; whole-air grab samples are used to confirm peak and typical inhalation exposures; and alveolar breath samples are used to confirm exposures and to estimate contaminant concentrations in the blood of the test subjects. While we do not suggest that this methodology should supersede any current investigative approach, this material is primarily offered as a consolidated reference to the many people or organizations who might contemplate a study of this type. Application of this investigative protocol should provide detailed exposure assessment information, while it supplies critical real world data for risk assessment specialists, toxicologists, and modeling experts. Data from a recent field study assessing exposures to trichloroethylene are presented to illustrate the utility and some of the limitations of this strategy.     

Reducing phosphorus flux from organic soils in surface flow treatment wetlands

Treatment wetlands have a finite period of effective nutrient removal after which treatment efficiency declines. This is due to the accumulation of organic matter which decreases the capacity and hydraulic retention time of the wetland. We investigated four potential solutions to improve the soluble reactive P (SRP) removal of a municipal wastewater treatment wetland soil including; dry down, surface additions of alum or calcium carbonate and physical removal of the accreted organic soil under both aerobic and anaerobic water column conditions. The flux of SRP from the soil to the water column under aerobic conditions was higher for the continuously flooded controls (1.1 ± 0.4 mg P m⁻² d⁻¹), dry down (1.5 ± 0.9 mg P m⁻² d⁻¹) and CaCO₃ (0.8 ± 0.7 mg P m⁻² d⁻¹) treatments while the soil removal and alum treatments were significantly lower at 0.02 ± 0.10 and −0.07 ± 0.02 mg P m⁻² d⁻¹, respectively. These results demonstrate that the two most effective management strategies at sequestering SRP were organic soil removal and alum additions. There are difficulties and costs associated with removal and disposal of soils from a treatment wetland. Therefore our findings suggest that alum addition may be the most cost effective and efficient means of increasing the sequestering of P in aging treatment wetlands experiencing reduced P removal rates. However, more research is needed to determine the longer term effects of alum buildup in the organic soil on the wetland biota, in particular, on the macrophytes and invertebrates. Since alum effectiveness is time limited, a longer term solution to P flux may favor the organic soil removal.     

CASE STUDIES OF AGRICULTURAL WATER CONSERVATION1

Farmers from four irrigation districts in Texas and California were questioned about water conservation practices they are now using, those they plan to adopt, and potential incentives that government might offer to induce still further water conservation on their part. While responses differed somewhat from place to place and among individual farmers, the general results were: a) farmers reported that “water conservation” is not new to them, it is something they practice regularly; b) recent innovations such as laser controlled land leveling devices have permitted some substantial water use reductions in recent years; and c) even greater incentive mechanisms that government could provide and that farmers would accept as useful incentives, such as long term low interest loans for water saving equipment, would probably not be able to reduce water use in agriculture much further than 15 percent below current levels. It is recommended nonetheless that Federal agencies and local water districts and individuals should nonetheless pursue water conservation training and education programs, demonstrations of conjunctive use and water banking opportunities for water saving, and increased loan programs for installation of water saving equipment.     

四川省部分豆科植物根瘤菌的遗传多样性

从四川省豆科植物鸡眼草属、合欢属、豇豆属、葛属、金合欢、杭子梢分离获得了103株根瘤菌,采用AFLP、BOXAIR-PCR研究了这些菌株的遗传多样性.结果表明,分离自四川省豆科植物6个属的根瘤菌存在明显的遗传多样性,AFLP分析中,全部供试菌株的相似性为21%,全部供试菌株可分为26个AFLP遗传群;BOXAIR-PCR聚类分析结果表明,103个菌株分在70%相似性水平处,供试菌株被分为18个BOX遗传群.除部分菌株外,多数根瘤菌按宿主类型聚群,同一宿主而地理来源不同的根瘤菌分布于不同的遗传群,表明宿主和地理环境对根瘤菌具有深刻影响.图3表1参9     

Simultaneous transport of parent and daughter compounds in aquifers with linear first-order sorption kinetics

In soils, daughter compounds may be generated from a parent compound by microbial metabolism, chemical reactions, radioactive decay, or other mechanisms. These daughter compounds are also acted upon by soil physical, chemical and biological processes. A system often referred to as a cascade or chain of compounds system results. While a great deal of attention has been given to this problem with the linear equilibrium assumption applied uniformly to all transport and reacting compounds, little attention has been given to the simultaneous transport and fate of a parent-daughter chain with a first-order rate assumed for the adsorption-desorption kinetics of each compound and with the soil partitioned into three sorption classes.A general one-dimensional cascade or chain model for the simultaneous transport of parent and daughter compounds in sorbing, homogeneous, water table aquifers is presented. The model is based on an advective-dispersive mass accounting formulation for both compounds and includes: (a) first-order rate of conversion of parent to daughter; (2) first-order rates of loss of either parent or daughter or both due to metabolism, chemical reaction and/or irreversible processes; (3) partitioning of the aquifer material into three sorption classes, namely mildly sorbing, strongly sorbing and organic matter; (4) linear first-order kinetic rules for adsorption and desorption operating on each of the sorbing soil fractions for each compound; (5) constantly emitting sources of rectangular shape of parent compound; and (6) mass accounting boundary conditions; and a tailorable initial distribution on [0, ∞). Mathematical analysis yields a coupled, linear system of equations including two transport and fate equations, initial and boundary data, and six kinetic rules, namely three each for parent and daughter compound. A numerical scheme for solving the system of equations was developed using readily available procedures since analytical solutions could not be found. Solutions for scenarios based on leaking underground sources are presented.     

Automatic potentiometric determination of dissolved oxygen

Commercially available automatic titration systems were tested in 1988 for potentiometric titration of liberated iodine by the Winkler method of oxygen determination. The potentiometric equivalence point was also compared to the manual starch end point. Finally the automatic method was used in order to estimate belowhalocline respiration in the Kattegat, Sweden. Standard deviations of 0.007 ml O₂ l^–1 or 0.1 to 0.3% coefficients of variation (% standard deviation of the mean) were achieved when titrating 25 ml from replicate 60-ml oxygen bottles using the automatic method, or 50 ml manually. The precision for replicate titrations of 50-ml aliquots of 0.001N KIO₃ was <0.05% (0.002 ml 0.01N Na₂S₂O₃) for the automatic method. Titration time for 25-ml aliquots was 2 to 4 min, somewhat longer than for manual titrations (1 to 1.5 min). However, during titration the operator is free to perform other tasks. It is not possible to use automatic sample changers, due to rapid iodine volatilization. The equipment can be handled by relatively unskilled analysts and is suitable for use on board research vessels or in field stations [weight for a Mettler^TM titrator (Mettler Instrumente AG, Greifensee, Switzerland) <10 kg, volume <0.1 m³]. Below-halocline oxygen consumption in the SE Kattegat ranged from 0 to 6 ml O₂ m^–3 h^–1 (mean values for September and October 1988=1.69 and 0.66 ml O₂ m^–3 h^–1, respectively, with 95% confidence limits of ca. ±0.6 ml O₂ m^–3 h^–1).     

Factors Influencing Allelopathy and Toxicity in Prymnesium parvum1

Granéli, Edna and Paulo S. Salomon, 2010. Factors Influencing Allelopathy and Toxicity in Prymnesium parvum. Journal of the American Water Resources Association (JAWRA) 46(1):108-120. Abstract: Some microalgae are able to kill or inhibit nutrient-competing microalgae, a process called allelopathy. Inhibiting or killing competitors enable these species to monopolize limiting resources, such as nitrogen and phosphorus. Prymnesium parvum is known to produce such allelopathic compounds, substances that seem identical to the ichthyotoxins identified from this species. Biotic and abiotic environmental factors influence not only growth rates but also toxin/allelopathic compounds production by P. parvum cells. Toxin production, as well as allelopathy, including grazer deterrence, increases dramatically in light, temperature, or nutrient stressed P. parvum cells. Correspondingly, toxicity and allelopathy may decrease, or cease completely, if cells are grown with high amounts of N and P in balanced proportions. However, even under nutrient (N and P) sufficient conditions, P. parvum is able to produce toxins/allelopathic compounds, with negative effects on other phytoplankton species or grazers, if cells densities of P. parvum are high relative to other species. This negative effect might shift the plankton community to more toxin resistant species. Filtrates from nutrient-deficient P. parvum cultures have almost the same strong negative effect on grazers and other phytoplankton species as when Prymnesium cells are grown together with the target organisms. Eutrophication, the increased input of N and P to aquatic ecosystems, besides increasing nutrient concentrations, is usually provoking unbalanced N:P condition for the optimal growth of phytoplankton, deviating from the Redfield ratio, i.e., the phytoplankton cellular nitrogen to phosphorus ratio, N:P = 16:1 (by atoms) or 7.2:1 (by weight). Eutrophication thus both enhances P. parvum growth and increases production of toxins and allelopathic compounds. Supplying N-deficient or P-deficient P. parvum cells with the deficient nutrient reduces toxicity to less than half within 24 h after additions. As P. parvum is mixotrophic, uptake of dissolved or particulate organic N (DON or PON) can also reduce toxicity and allelopathy in the same manner as addition of inorganic N to N-starved cells. In conclusion, P. parvum, by increasing its toxicity and allelopathic ability under poor environmental conditions, outcompetes the co-occurring phytoplankton species.     

Pilot scale application of a method for the analysis of perfluorinated compounds in surface soils

A growing number of studies now indicate that perfluorinated compounds (PFCs) are globally distributed in the environment. Their widespread distribution and presence in remote locations has led to questions about the importance of atmospheric and oceanic transport. Describing their distribution in surface soils is also an essential but neglected element in developing a comprehensive understanding of their occurrence in the environment. Soils are the critical link between global atmospheric and hydrologic processes where both local and distant contaminants can accumulate and be released into aquatic and terrestrial communities. Because PFC concentrations in soils will influence ground and surface water, wildlife, and crops, methods to accurately measure PFCs in soil are clearly needed. To help answer this need, we developed a method for the analysis of nine perfluorinated carboxylic acids and four perfluorinated sulfonic acids in soil. Samples from six nations (n = 10 per nation) were analyzed by LC-MS/MS to demonstrate the method performance parameters and to make preliminary observations about the occurrence of the PFCs in soils in different parts of the world. The resulting method shows acceptable performance characteristics for the target compounds in most soils while documenting the widespread occurrence of PFCs in surface soils.     

Influence of Prey and Nutritional Status on the Rate of Nitrogen Uptake by Prymnesium parvum (haptophyte)1

Lindehoff, Elin, Edna Granéli, and Patricia M. Glibert, 2010. Influence of Prey and Nutritional Status on the Rate of Nitrogen Uptake by Prymnesium parvum (Haptophyte). Journal of the American Water Resources Association (JAWRA) 46(1):121-132. DOI: 10.1111/j.1752-1688.2009.00396.x Abstract: We studied how the specific nitrogen (N) uptake rates of nitrate (NO₃⁻), urea, and the amino acids, glutamic acid and glycine, by Prymnesium parvum were affected by (1) the change from N-deficient status to N-sufficient status of the P. parvum cells, (2) presence of prey from a natural Baltic Sea plankton community, and (3) the composition of prey as affected by additions of terrestrial originated dissolved organic matter (DOM) or inorganic nutrients. Nitrogen-deficient P. parvum (16 μM NO₃⁻ and 4 μM PO₄⁻, molar N:P ratio of 4:1) were mixed with a natural Baltic plankton community and given PO₄³⁻ and (1) NO₃⁻ (control) or (2) high molecular weight DOM, >1 kDa concentrated from sewage effluent (+DOM), in a molar N:P ratio of 9-10:1. With additions of ¹⁵N-enriched substrates, rates of N uptake from NO₃⁻, urea, and the amino acids glycine and glutamic acid were measured every 24 h for 72 h. Initial N-deficient P. parvum were highly toxic (3.7 ± 0.9 × 10⁻⁴ mg Sap equiv/cell) and toxic allelochemicals were released into the medium causing the natural plankton community to lyse. Rates of N uptake differed between the “control” and the “+DOM” treatments over time; total (sum of the N substrates measured) absolute uptake rates (ρ_cell, fmol N/cell/h) at ambient culture conditions were significantly higher (ANOVA, p < 0.05) in the more toxic “control” treatments compared with the “+DOM” treatments after 48 h. In the “control” treatment, the total ρ_cell increased significantly (ANOVA, p < 0.01) from time 0 to 48 h, while in the “+DOM” treatment there was no significant increase. Released organic nutrients from the lysed plankton cells may have increased uptake rates of amino acids and urea by P. parvum. All uptake rates declined in all treatments by 72 h. Total dissolved N uptake rates at ambient culture conditions were estimated to make up about 10% of the N P. parvum are potentially capable of ingesting from particulate prey.