Percentile estimation using variable censored data

Much progress has been made in recent years to address the estimation of summary statistics, using data that are subject to censoring of results that fall below the limit of detection (LOD) for the measuring instrument. Truncated data methods (e.g., Tobit regression) and multiple-imputation are two approaches for analyzing data results that are below the LOD. To apply these methods requires an assumption about the underlying distribution of the data. Because the log-normal distribution has been shown to fit many data sets obtained from environmental measurements, the common practice is to assume that measurements of environmental factors can be described by log-normal distributions. This article describes methods for obtaining estimates of percentiles and their associated confidence intervals when the results are log-normal and a fraction of the results are below the LOD. We present limited simulations to demonstrate the bias of the proposed estimates and the coverage probability of their associated confidence intervals. Estimation methods are used to generate summary statistics for 2,3,7,8-tetrachloro dibenzo-p-dioxin (2,3,7,8-TCDD) using data from a 2001 background exposure study in which PCDDs/PCDFs/cPCBs in human blood serum were measured in a Louisiana population. Because the congener measurements used in this study were subject to variable LODs, we also present simulation results to demonstrate the effect of variable LODs on the multiple-imputation process.     

Uptake and accumulation of cadmium, lead and zinc by Siam weed [Chromolaena odorata (L.) King & Robinson

The Siam weed, Chromolaena odorata (L.) King & Robinson, Family Asteraceae, was found to be a new Pb hyperaccumulator by means of field surveys on Pb soil and hydroponic studies. Plants from field collection accumulated 1377 and 4236mgkg(-1) Pb in their shoots and roots, respectively, and could tolerate soil Pb concentrations up to 100000 mgkg(-1) with a translocation factor of 7.62. Very low concentrations of Cd and Zn were found in plants collected from the field. Under nutrient solution culture condition, C. odorata from the contaminated site (CS) and from non-contaminated site (NCS) grew normally with all three metals (Pb, Cd, Zn) supplied. However, the relative growth rates of all treated plants decreased with increased metal concentrations. The percentage uptakes of Pb, Cd, and Zn by C. odorata increased with increasing metal concentrations. Pb concentration in shoots and roots reached its highest values (1772.3 and 60655.7mgkg(-1), respectively) at a Pb supply level of 10mgl(-1). While the maximum concentrations of Cd (0.5mgl(-1)) in shoots and roots of C. odorata were 102.3 and 1440.9mgkg(-1), and the highest concentrations of Zn (20mgl(-1)) were 1876.0 and 7011.8mgkg(-1), respectively. The bioaccumulation coefficients of Pb and Cd were greater than 1000. These results confirm that C. odorata is a hyperaccumulator which grows rapidly, has substantial biomass, wide distribution and has a potential for the phytoremediation of metal contaminated soils.     

Binding affinity of proanthocyanidin from waste Pinus radiata bark onto proline-rich bovine achilles tendon collagen type I

Binding affinity of proanthocyanidin (PA) purified from Pinus radiata bark waste onto bovine Achilles tendon collagen (type I) was studied. Adsorption of PA onto the collagen was optimized by examining pH, contact time and temperature. The adsorption was pH-dependent. The maximum adsorption capacity (Q(0)) of PA on collagen was found to be 211 mg g(-1) using the Langmuir isotherm. Comparison between two adsorbents also showed that collagen had higher adsorptivity of approximately 20% more than PVPP (polyvinyl polypyrrolidone). The high affinity between PA and collagen was further confirmed in solvent solubility experiments. The observed solvent resistance was thought to be mainly due to a hydrophobic stacking mechanism reinforced by hydrogen bonding. FT-IR spectra clearly indicated the presence of PA adsorbed on collagen. The results have interesting implications that PA can be a good protective agent for collagen against collagenase and other enzymes.     

Estimates of ambient background concentrations of trace metals in soils for risk assessment

Site-specific or soil type-specific ambient background concentrations (ABCs) of trace metals in soils are needed for risk assessment. We investigated three different methods for estimating ABCs in soils using a dataset of 5691 soil samples from England and Wales. The concentrations of Co, Cr and Ni were strongly associated with Al and Fe, and multiple regressions explained 62-85% of their variation, and Al and Fe can therefore be used to predict ABCs for these metals. Soil texture had a major influence on the concentrations of Cd, Co, Cr, Cu, Ni and Zn, and the medians were 3-5 fold higher in clayey than in sandy soils. This was used to predict texture-specific ABCs. Lead concentration was higher in acidic peaty soils than in other soils. A probability graph method was used to estimate ABC for Pb in a population of relatively uncontaminated soils. Potential applications of ABCs are discussed.     

Challenges in quantifying biosphere-atmosphere exchange of nitrogen species

Recent research in nitrogen exchange with the atmosphere has separated research communities according to N form. The integrated perspective needed to quantify the net effect of N on greenhouse-gas balance is being addressed by the NitroEurope Integrated Project (NEU). Recent advances have depended on improved methodologies, while ongoing challenges include gas-aerosol interactions, organic nitrogen and N(2) fluxes. The NEU strategy applies a 3-tier Flux Network together with a Manipulation Network of global-change experiments, linked by common protocols to facilitate model application. Substantial progress has been made in modelling N fluxes, especially for N(2)O, NO and bi-directional NH(3) exchange. Landscape analysis represents an emerging challenge to address the spatial interactions between farms, fields, ecosystems, catchments and air dispersion/deposition. European up-scaling of N fluxes is highly uncertain and a key priority is for better data on agricultural practices. Finally, attention is needed to develop N flux verification procedures to assess compliance with international protocols.     

Seasonal Variation of Toxic Benzene Emissions in Petroleum Refinery

Petroleum refineries are largest chemical industries that are responsible for the emission of several pollutants into the atmosphere. Benzene is among the most important air pollutants that are emitted by petroleum refineries, since they are involved in almost every refinery process. Volatile organic compounds (VOCs) are a major group of air pollutants, which play a critical role in atmospheric chemistry. These contribute to toxic oxidants, which are harmful to ecosystem, human health and atmosphere. The variability of pollutants is an important factor in determining human exposure to these chemicals. The ambient air concentrations of benzene were measured in several sites around the Digboi petroleum refinery, near the city of Gowahati in northeast India, during winter and summer 2004. The seasonal and spatial variations of the ambient air concentrations of this benzene were investigated and analyzed. An estimation of the contribution of the refinery to the measured atmospheric levels of benzene was also performed. The ambient air mixing ratios of benzene in a large area outside the refinery was generally low, in ppbv range, much lower than the ambient air quality standards. This article presents the temporal and spatial variation of air pollution in and around petroleum refinery and showed that no health risk due to benzene is present in the areas adjacent to the refinery.     

Photodegradation of organophosphorus insecticides - investigations of products and their toxicity using gas chromatography-mass spectrometry and AChE-thermal lens spectrometric bioassay

Four organophosphorus compounds: azinphos-methyl, chlorpyrifos, malathion and malaoxon in aqueous solution were degraded by using a 125 W xenon parabolic lamp. Gas chromatography-mass spectrometry (GC-MS) was used to monitor the disappearance of starting compounds and formation of degradation products as a function of time. AChE-thermal lens spectrometric bioassay was employed to assess the toxicity of photoproducts. The photodegradation kinetics can be described by a first-order degradation curve C=C0e(-kt), resulting in the following half lives: 2.5min for azinphos-methyl, 11.6 min for malathion, 13.3 min for chlorpyrifos and 45.5 min for malaoxon, under given experimental conditions. During the photoprocess several intermediates were identified by GC-MS suggesting the pathway of OP degradation. The oxidation of chlorpyrifos results in the formation of chlorpyrifos-oxon as the main identified photoproduct. In case of malathion and azinphos-methyl the corresponding oxon analogues were not detected. The formation of diethyl (dimethoxy-phosphoryl) succinate in traces was observed during photodegradation of malaoxon and malathion. Several other photoproducts including trimethyl phosphate esters, which are known to be AChE inhibitors and 1,2,3-benzotriazin-4(3H)-one as a member of triazine compounds were identified in photodegraded samples of malathion, malaoxon, and azinphos-methyl. Based on this, two main degradation pathways can be proposed, both result of the (P-S-C) bond cleavage taking place at the side of leaving group. The enhanced inhibition of AChE observed with the TLS bioassay during the initial 30 min of photodegradation in case of all four OPs, confirmed the formation of toxic intermediates. With the continuation of irradiation, the AChE inhibition decreased, indicating that the formed toxic compounds were further degraded to AChE non-inhibiting products. The presented results demonstrate the importance of toxicity monitoring during the degradation of OPs in processes of waste water remediation, before releasing it into the environment.     

Advanced oxidation processes for the treatment of olive-oil mills wastewater

In this work, the treatment of an actual industrial waste with three advanced oxidation processes (AOP) has been studied: conductive-diamond electrooxidation (CDEO), ozonation and Fenton oxidation. The wastewater comes from olive-oil mills (OMW) and contains a COD of nearly 3000 mg dm(-3). CDEO allowed achieving the complete mineralization of the waste with high current efficiencies. Likewise, both ozonation and Fenton oxidation were able to treat the wastes, but they obtained very different results in terms of efficiency and mineralization. The accumulation of oxidation-refractory compounds as final products excludes the use of ozonation and Fenton oxidation as a sole treatment technology. This confirms that besides the hydroxyl-radical mediated oxidation, CDEO combines other important oxidation processes such as the direct electro-oxidation on the diamond surface and the oxidation mediated by other electrochemically formed compounds generated on this electrode.     

Lichen and moss bags as monitoring devices in urban areas. Part II: trace element content in living and dead biomonitors and comparison with synthetic materials

Lobes of the lichen Pseudevernia furfuracea (L.) Zopf and shoots of the moss Hypnum cupressiforme Hedw. were subjected to different treatments (water washing, oven drying, HNO3 washing, NH4-oxalate extraction) to assess the influence of vitality on accumulation efficiency, during a 6-week exposure in bags in two Italian cities, Trieste and Naples. No trend emerged between treatments, in terms of accumulation ability, for major and trace elements. Only water-washed lichens showed an increased C and N content after exposure in both cities. Element concentrations generally reached higher values in mosses than in lichens, especially for Al, Fe, and Zn (both cities), and for Cu, Mg and Na (Naples). Surface development strongly influenced accumulation capacity of the biomonitors. Quartzose and cation exchange filters revealed, on a weight basis, a poor performance. In urban environments, surface interception of atmospheric particulate seems to play a major role in accumulation, irrespective of organism vitality.     

Dynamic responses of photosystem II in the Namib Desert shrub, Zygophyllum prismatocarpum, during and after foliar deposition of limestone dust

The effects of limestone dust deposition on vegetation in desert ecosystems have not yet been reported. We investigated these effects in a succulent shrub from the Namib Desert at a limestone quarry near Skorpion Zinc mine (Namibia). Effects of limestone dust were determined in Zygophyllum prismatocarpum (dollar bush) plants with heavy, moderate and no visible foliar dust cover by means of chlorophyll a fluorescence measurements. Limestone dust deposition decreased overall plant performance through loss of chlorophyll content, inhibition of CO(2) assimilation, uncoupling of the oxygen-evolving complex and decreased electron transport. Importantly, dynamic recovery occurred after termination of limestone extraction at the quarry. Recovery was accelerated by rainfall, mainly because of dust removal from leaves and stimulation of new growth. These results indicate that limestone dust has severe effects on photosynthesis in desert shrubs, but that recovery is possible and that, in arid environments, this process is modulated by rainfall.