Correction methods for organic carbon artifacts when using quartz-fiber filters in large particulate matter monitoring networks: the regression method and other options

Sampling and handling artifacts can bias filter-based measurements of particulate organic carbon (OC). Several measurement-based methods for OC artifact reduction and/or estimation are currently used in research-grade field studies. OC frequently is not artifact-corrected in large routine sampling networks (e.g., U.S. Environmental Protection Agency (EPA)'s Chemical Speciation Network). In some cases, the OC artifact has been corrected using a regression method (RM) for artifact estimation. In this method, the gamma-intercept of the regression of the OC concentration on the fine particle (PM2.5) mass concentration is taken to be an estimate of the average OC sampling artifact (net of positive and negative artifacts). This paper discusses options for artifact correction in large routine sampling networks. Specifically, the goals are to (1) articulate the assumptions and limitations inherent to the RM, (2) describe other artifact correction approaches, and (3) suggest a cost-effective method for artifact correction in large monitoring networks. The RM assumes a linear relationship between measured OC and PM mass: a constant slope (OC mass fraction) and a constant intercept (RM artifact estimate). These assumptions are not always valid. Additionally, outliers and other individual data points can have a large influence on the RM artifact estimates. The RM yields results within the range of measurement-based methods for some datasets and not for others. Given that the adsorption of organic gases increases with atmospheric concentrations of organics, subtraction of an average artifact from all samples (e.g., across multiple sites) will underestimate OC for lower-concentration samples (e.g., clean sites) and overestimate OC for higher-concentration samples (e.g., polluted sites). For relatively accurate, simple, and cost-effective artifact OC estimation in large networks, the authors suggest backup filter sampling on at least 10% of sampling days at all sites with artifact correction on a sample-by-sample basis as described herein.     

Establishment of a constructed wetland in extreme dryland

Background, aim, and scope

The project was set to construct an extensive wetland in the southernmost region of Israel at Kibbutz Neot Smadar (30°02′45″ N and 35°01′19″ E). The results of the first period of monitoring, summary, and perspectives are presented. The constructed wetland (CW) was built and the subsequent monitoring performed in the framework of the Southern Arava Sustainable Waste Management Plan, funded by the EU LIFE Fund. The specific aims were: (1) To end current sewage disposal and pollution of the ground, the aquifer, and the dry river bed (wadi) paths by biologically treating the sewage as part of the creation of a sustainable wetland ecosystem. (2) Serve as an example of CW in the Negev highlands and the Arava Valley climates for neighboring communities and as a test ground for plants and building methods appropriate to hyper arid climate. (3) Serve as an educational resource and tourist attraction for groups to learn about water reuse, recycling, local wildlife and migrating birds, including serving the heart of a planned Ecological–Educational Bird Park. This report is intended to allow others who are planning similar systems in hyper arid climates to learn from our experience.

Materials and methods

The project is located in an extreme arid desert with less than 40 mm of rain annually and temperature ranges of ?5°C to +42°C. The site receives 165–185 m³ of municipal and agricultural wastes daily, including cowshed and goat wastes and winery outflow.

Results

The CW establishment at Neot Smadar was completed in October 2006. For 8 months, clean water flowed through the system while the plants were taking root. In June 2007, the wetland was connected to the oxidation pond and full operation began. Because of seepage and evaporation, during the first several months, the water level was not high enough to allow free flow from one bed to the next. To bed A, the water was pumped periodically from the oxidation pond (Fig. 1) and from there flowed by gravitation through the rest of the system. The initial results of the monitoring are promising. In nearly all measurements, the system succeeded as expected to reduce levels of contaminants at least to the level acceptable for irrigating fruit trees and often to the level of unlimited irrigation. The introduction of the plants in the system and their physiological performance were evaluated and were found to correlate well to the quality of water in the various beds.

Discussion

It should be said at the outset that evaluation of the performance of a CW system is a long-term process. Thus, the main aim of this report is to present the problems, difficulties, preliminary results, and concepts concerned with the first stage of establishment of CW in an extremely dry region.

Conclusions

The CW system was designed to dispose of municipal and agricultural wastes in a way that not merely reduces pollution, but adds to environmental quality by creating accessible parkland for local residents and tourists. Several factors affected the performance of the system at the initial stages of operation: ecological balance between microbes and plants, big seasonal variations, seepage and evaporation reduced the flow in the initial operation of the system. Despite the initial difficulties, the quality of water coming out the system is acceptable for irrigation.

Recommendations and perspectives

The CW can function well under extreme dryland conditions. The oxidation pond was the major source of evaporation and bad odors. Therefore, alternatives to the oxidation pond are needed. Cost effectiveness of the system still has to be evaluated systematically.     

Substance-related environmental monitoring

Background  Due to the requirements of the EU Water Framework Directive and other legal regulations (e.g., national laws like the German Federal Soil Protection Act), but also due to the implementation of the new EU chemicals management system REACH, environmental monitoring will gain increasing importance for the surveillance of environmental quality as well as for the assessment of chemicals. Against this background, the Work Group on ‘Environmental Monitoring’ of the Division of ‘Environmental Chemistry and Ecotoxicology’ within the German Chemical Society has compiled a position paper on substance-related environmental monitoring. Scope  Core elements of this position paper are the definitions of important terms like monitoring, exposure monitoring, effect monitoring, and integrated monitoring. Moreover, temporal and spatial aspects (monitoring of spatial distributions, trend monitoring, and retrospective monitoring) and their applications are discussed. The main focus of this position paper is the coverage of aspects which have to be observed for the preparation and implementation of a monitoring program. Essential is the clear specification of the targets of the monitoring which determine the development of the monitoring concept and its realization, e.g., if environmental media (compartments) or organisms are most appropriate as samples for the aim of the study. Of course, also the properties of the target substances are important (e.g., lipophilicity/bioaccumulation as pre-requisite for an exposure monitoring with organisms). Finally, the monitoring phases of sample planning, sampling, storage and transport of samples, selection of analytical methods, quality assurance measures as well as reporting are discussed. Perspectives  An important issue for the future is to link the quantification of chemicals in environmental compartments (exposure and pollution monitoring) more closely to the study of biological effects (effect monitoring) than has been the case up to now. Furthermore, by inclusion of a spatial differentiation, a comprehensive evaluation of the state of an ecosystem can be obtained and the relevance of the results improved. Practical examples of monitoring studies which illustrate various aspects covered in this position paper will be presented in a series of publications by members of the Work Group in the following issues of this journal.

The toxicity of sulfamethazine to Daphnia magna and its additivity to other veterinary sulfonamides and trimethoprim

Sulfonamides (SAs), the oldest chemotherapeutic agents used for antimicrobial therapy, still play an important role in veterinary mass treatments. Consequently, traces of these compounds, alone or in combinations, have been repeatedly detected in the environment. Sulfamethazine (SMZ) deserves particular attention not only because it is the most used veterinary SA, but also due to its proven effects on fertility in mice and on thyroid hormone homeostasis in rats. In this study, after evaluating the acute toxicity to Daphnia magna of six veterinary SAs and trimethoprim (TMP), the additivity of SMZ to each other compound was tested using the isobologram method. Two reproduction tests on the same biological model were also performed in order to derive LOEC and NOEC of SMZ. The acute EC₅₀ was in the range 131–270 mg L⁻¹ for all the compounds tested with the exception of sulfaguanidine (EC₅₀ = 3.86 mg L⁻¹). In acute binary tests SMZ showed a complex interaction with sulfaquinoxaline (superadditivity, additivity or subadditivity) at the three different combination ratios tested, simple additivity to TMP and less than additive interaction when paired to the other SAs. LOEC and NOEC of SMZ obtained from reproduction tests were 3.125 and 1.563 mg L⁻¹, respectively. In conclusion, SMZ should not harm the crustacean population at environmentally realistic concentrations. Its toxicity is comparable to that of other systemic SAs, and their binary interactions are less than additive. The same can not be entirely said for enteric SAs, and considering that these compounds are administered at high doses and mostly excreted in unmetabolised form, further evaluation of their impact to the aquatic environment seems advisable.     

A Monte-Carlo Simulation of the Ozone Attainment Process

A Monte-Carlo simulation of the approach to attainment of the National Ambient Air Quality Standard for ozone has been performed for the California Bay Area Air Quality Management District. Four compliance tests together with different design values are used in the simulation. The results show that the present compliance test requiring a zero-percent chance of violation and the design value represented by the fourth highest value in three years makes both the standard and the control requirement much more stringent than generally assumed. In fact, to attain the standard on a long-term basis would require annual means and annual second-highest values that are close to those of the rural background ozone. The simulation also shows that by taking into account the fluctuation of ozone concentrations in the compliance test, such as a t test, and by using a design value consistent with the test, a standard defined in terms of the three-year mean of the annual second-highest values not only is more consistent with the currently- perceived stringency of the present standard, but may also be attainable with a more reasonable control requirement.     

Ecotoxicity and biodegradability of antielectrostatic dicephalic cationic surfactants

Four series of dicephalic cationic surfactants, considered as new antielectrostatic agents have been investigated in order to establish their toxicity and biodegradability. Among them N,N-bis[3,3′-(dimethylamine)propyl]alkylamides, N,N-bis[3,3′-(dimethylamine)propyl]alkylamide dihydrochlorides, N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dibromides and N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dimethylsulphates with different hydrophobic chain length (n-C₉H₁₉ to n-C₁₅H₃₁) and type of counterion (chloride, bromide and methylsulfate) have been studied. The inhibitory effect against microorganisms has been examined using model gram-positive and gram-negative bacteria, and yeasts. None of the tested surfactants have shown antimicrobial activity against gram-negative bacteria (Escherichia coli, Pseudomonas putida) and yeasts (Saccharomyces cerevisiae, Rhodotorula glutinis) at a concentration below 1000 μg mL⁻¹, however some of them were moderately active against gram-positive bacteria (Staphylococcus aureus, Bacillus subtilis). The Microtox® test was successfully applied to measure EC₅₀ values of the studied dicephalic cationic surfactants. Their toxicity to Vibrio fischeri depended upon the alkanoyl chain length with the EC₅₀ values in a range of 2.6-980 mg L⁻¹. N,N-bis[3,3′-(dimethylamine)propyl]alkylamide dihydrochlorides 2a-b and N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dibromides 3a-b comprising n-decanoyl and n-dodecanoyl hydrophobic tails appeared to be the least toxic. Furthermore, the biodegradability under aerobic conditions of 2a-b, 3a-b was evaluated using OECD Method 301F. According to the obtained results 2a, 3a-3b can be considered as almost readily biodegradable and they are not expected to be persistent in the environment. Additionally, partial biodegradation was observed for 2b, indicating its possible biodegradation in wastewater treatment systems.     

Examination of the Enzyme Resistance of Polyurethane Powder Coatings

Polyurethanes powder lacquers were obtained in a reaction hydroxy terminated polyester resin RUCOTE 102 and blocked polyisocyanate crosslinkers. The polyisocyanates were synthesized using alicyclic diisocyanates (IPDI and H₁₂MDI) and monohydric aliphatic alcohols as well as dibutyltin dilaurate and triethylamine as a catalysts. The biodegradation experiments were realized in solution consisted of lipase (Novozym 735, Novozym 51,032, Lipolase 100L or Palatase 20,000) and phosphate buffer during 42 days at 37 °C. The biodegradation progress was controlled by using optical microscopy method, thermal analysis TG/DTA, DSC method, surface free energy parameters, total organic carbon measurements and sample weight loss. The three-dimensional surface topography of the powder lacquers by means of confocal microscope was investigated. The values of surface roughness parameters were calculated.     

Thirty-year trends in suspended sediment in seven Lake Erie tributaries

Sediment is an important pollutant for Lake Erie and its tributaries as a carrier of other substances and as a pollutant in its own right. Environmental managers have called for major reductions in sediment loadings in Lake Erie tributaries. In this study, 30-yr (1975-2005) datasets with daily resolution are analyzed to identify and interpret trends in sediment concentrations and loads in major US tributaries to Lake Erie. The Maumee and Sandusky Rivers in agricultural northwest Ohio show continual decreases throughout this period, but the River Raisin shows increases, especially in the last decade. The urban and forested Cuyahoga River shows little trend before 2000 but shows increases since then. The mostly forested Grand River shows strong decreases before 1995, little change thereafter until the early 2000s, and then increases. In most cases, the greatest decreases or smallest increases, depending on the river, are associated with summer and fall and with low flow conditions, whereas the smallest decreases or greatest increases are associated with the spring and with high flow conditions. Analysis of concentration-flow relationships indicates that these changes are not due to weather but reflect positive and negative anthropogenic influences. Sediment decreases in the northwestern Ohio tributaries seem to reflect the successful use of agricultural practices to reduce erosion and prevent sediment loss. Opportunities for further reductions in sediment loads and concentrations lie in better management of sediment losses during winter and spring.