KALMAN FILTER CALCULATION OF SAMPLING FREQUENCY WHEN DETERMINING ANNUAL MEAN SOLUTE CONCENTRATIONS

ABSTRACT: A linear filter (Kalman filter) technique was used with a Streamflow-concentration model the minimize surface water quality sampling frequencies when determining annual mean solute concentrations with a predetermined allowable error. The Kalman filter technique used the stream discharge interval as a replacement for the more commonly used time interval. Using filter computations, the measurement error variance was minimized within the sample size constraints. The Kalman filter application proposed here is applicable only under several conditions including: monitoring is solely to estimate annual mean concentration; discharge measurement errors are negligible; the Streamflow-concentration model is valid; and monthly samples reflect the total variance of the solute in question.     

Matrix effect on the performance of headspace solid phase microextraction method for the analysis of target volatile organic compounds (VOCs) in environmental samples

Solid phase microextraction (SPME) is a fast, cheap and solvent free methodology widely used for environmental analysis. A SPME methodology has been optimized for the analysis of VOCs in a range of matrices covering different soils of varying textures, organic matrices from manures and composts from different origins, and biochars. The performance of the technique was compared for the different matrices spiked with a multicomponent VOC mixture, selected to cover different VOC groups of environmental relevance (ketone, terpene, alcohol, aliphatic hydrocarbons and alkylbenzenes). VOC recovery was dependent on the nature itself of the VOC and the matrix characteristics. The SPME analysis of non-polar compounds, such as alkylbenzenes, terpenes and aliphatic hydrocarbons, was markedly affected by the type of matrix as a consequence of the competition for the adsorption sites in the SPME fiber. These non-polar compounds were strongly retained in the biochar surfaces limiting the use of SPME for this type of matrices. However, this adsorption capacity was not evident when biochar had undergone a weathering/aging process through composting. Polar compounds (alcohol and ketone) showed a similar behavior in all matrices, as a consequence of the hydrophilic characteristics, affected by water content in the matrix. SPME showed a good performance for soils and organic matrices especially for non-polar compounds, achieving a limit of detection (LD) and limit of quantification (LQ) of 0.02 and 0.03 ng g⁻¹ for non-polar compounds and poor extraction for more hydrophilic and polar compounds (LD and LQ higher 310 and 490 ng g⁻¹). The characteristics of the matrix, especially pH and organic matter, had a marked impact on SPME, due to the competition of the analytes for active sites in the fiber, but VOC biodegradation should not be discarded in matrices with active microbial biomass.     

The effects of soil amendments on heavy metal bioavailability in two contaminated Mediterranean soils

Two heavy metal contaminated calcareous soils from the Mediterranean region of Spain were studied. One soil, from the province of Murcia, was characterised by very high total levels of Pb (1572 mg kg(-1)) and Zn (2602 mg kg(-1)), whilst the second, from Valencia, had elevated concentrations of Cu (72 mg kg(-1)) and Pb (190 mg kg(-1)). The effects of two contrasting organic amendments (fresh manure and mature compost) and the chelate ethylenediaminetetraacetic acid (EDTA) on soil fractionation of Cu, Fe, Mn, Pb and Zn, their uptake by plants and plant growth were determined. For Murcia soil, Brassica juncea (L.) Czern. was grown first, followed by radish (Raphanus sativus L.). For Valencia soil, Beta maritima L. was followed by radish. Bioavailability of metals was expressed in terms of concentrations extractable with 0.1 M CaCl2 or diethylenetriaminepentaacetic acid (DTPA). In the Murcia soil, heavy metal bioavailability was decreased more greatly by manure than by the highly-humified compost. EDTA (2 mmol kg(-1) soil) had only a limited effect on metal uptake by plants. The metal-solubilising effect of EDTA was shorter-lived in the less contaminated, more highly calcareous Valencia soil. When correlation coefficients were calculated for plant tissue and bioavailable metals, the clearest relationships were for Beta maritima and radish.     

Duckweed (Lemna gibba) growth inhibition bioassay for evaluating the toxicity of olive mill wastes before and during composting

Two-phase olive mill waste (TPOMW) is considered the main problem confronting the modern oil extraction and processing industry. Composting has been recently proposed as a suitable method to treat TPOMW so that it is suitable for use in agriculture. In the work reported here, the Lemna gibba bioassay was tested to assess the toxicity of TPOMW before and during the composting process. The method was compared with the Lepidium sativum bioassay and with other chemical maturity indices traditionally reported in the literature. The L. gibba test proved to be a simple, sensitive, and accurate method to evaluate toxicity before and during the composting of TPOMW. Plant growth response was measured by two methods: counting the number of fronds (leaves) and measuring total frond area (TFA) with image analysis software. Compared to the counting of fronds (L. gibba) or seeds (L. sativum), the use of area-measuring software permitted a very rapid, unbiased and easy way of analysing the toxicity of TPOMW before and during composting. Although the accuracy of the frond count method was similar to the traditional cress seed test, data analysis showed that the TFA measurement method was statistically more accurate (significantly lower variance) than the frond count approach. Highly significant correlations were found between TFA and some important maturation indices commonly reported in literature indicating that the L. gibba bioassay can be a useful tool to determine the degree of maturity of TPOMW composts.     

Spatiotemporal analysis of traffic emissions in over 5000 municipal districts in Brazil

Exposure to traffic emission is harmful to human health. Emission inventories are essential to public health policies aiming at protecting human health, especially in areas with incomplete or nonexistent air pollution monitoring networks. In Brazil, for example, only 1.7% of municipal districts have a monitoring network, and only a few studies have reported data on vehicle emission inventories. No studies have presented emission inventories by municipality. In this study, we predicted vehicular emissions for 5570 municipal districts in Brazil during the period 2001–2012. We used a top-down method to estimate emissions. Carbon dioxide (CO₂) is the pollutant with the highest emissions, with approximately 190 million tons per year during the period 2001–2012). For the other traffic-related pollutants, we predicted annual emissions of 1.5 million tons for carbon monoxide (CO), 1.2 million tons of nitrogen oxides (NO_x), 209,000 tons of nonmethane hydrocarbons (NMHC), 58,000 tons of particulate matter (PM), and 42,000 tons for methane (CH₄). From 2001 to 2012, CO, NMHC, and PM emissions decreased by 41, 33, and 47%, respectively, whereas those CH₄, NO_x, and CO₂ increased by 2, 4, and 84%, respectively. We estimated uncertainties in our study and found that NO_x was the pollutant with the lowest percentage difference, 8%, and NMHC with the highest one, 30%. For CO, CH₄, CO₂, and PM, the values were 22, 14, 21, and 20%, respectively. Finally, we found that during 2001 and 2012 emissions increased in the Northwest and Northeast. In contrast, pollutant emissions, except for CO₂, decreased in the Southeast, South, and part of Midwest. Our predictions can be critical to efforts developing cost-effective public policies tailored to individual municipal districts in Brazil.

Implications: Emission inventories may be an alternative approach to provide data for air quality forecasting in areas where air quality data are not available. This approach can be an effective tool in developing spatially resolved emission inventories.     

Audits and root cause analysis

Many current audit programs are very good at determining the compliance issues at a site, but are less successful in developing long-term compliance solutions. One method for addressing these issues is the use of root cause analysis techniques. These techniques allow the facility to identify and focus on permanent solutions to compliance issues. The authors note the following: Conducting a root cause analysis is not a substantial burden on the audit team or the facility. Most information is already collected during the audit, but is not being used. Looking at the overview pattern of the root cause analysis can provide a picture of the maturity of your audit program. Pareto charts are excellent methods to convey the results of your analysis. They show both the trends of analysis and help highlight the most significant root causes.     

Influence of olive mill wastewater in composting and impact of the compost on a Swiss chard crop and soil properties

The suitability of olive mill wastewater (OMW) for composting was studied by the addition of this liquid waste to a mixture of cotton gin waste and sewage sludge, and its composting was compared with that of another pile of similar composition, but without olive mill wastewater. Both piles were composted by the Rutgers static pile system in a pilot plant. To study the effects of both composts on plant yield and soil properties, a plot experiment was carried out with Swiss chard (Beta vulgaris L. var. cicla). Five treatments were applied: mineral fertiliser and two doses (30 and 60 tons ha(-1)) of both composts. The olive mill wastewater addition produced a compost with lower organic matter and nitrate concentrations, higher electrical conductivity, and a stabilised and humified organic matter similar to that of the compost produced without olive mill wastewater. The olive mill wastewater compost application to soil did not injure plants, producing a similar plant yield to both compost without olive mill wastewater and inorganic fertiliser. Also, the accumulation of potentially toxic heavy metals in plants cultivated with organic or mineral fertilisers did not reveal significant differences. The olive mill wastewater compost application to soil also improved the chemical and physicochemical properties of the soil.     

Soil mineralization of two-phase olive mill wastes: effect of the lignocellulosic composition on soil C dynamics

The low degradation rate of two-phase olive mill wastes (TPOMW) during composting and after soil application is a characteristic feature of these materials. The aim of this work was to evaluate the relationship between the lignocellulosic fraction of TPOMW and the organic matter (OM) degradation rate in three agricultural soils amended with four TPOMW composting mixtures at different degree of stabilisation and prepared with different bulking agents and N sources. The mineralisation kinetics of TPOMW composting mixtures in soil reflected a large amount of slowly mineralisable C even in the starting mixtures (I and T1) where this fraction represented up to 85% of the total potentially mineralisable C pool. The effect of rich lignocellulosic composition was confirmed by the study of the DTS (50% dry TPOMW + 50% sheep manure) mixtures prepared with dry TPOMW, which had undergone partial degradation in a storage pond for one year before composting. These DTS samples showed a more similar kinetic behaviour in soil than the more transformed composting mixtures as reflected in the principal component analysis (PCA) diagram, where they were grouped in the same quadrant dominated by the lignin/holocellulose ratio. Soils amended with mature composts evolved very low amounts of C (between 2 and 6% of the added C) after two months of incubation, which highlights the suitability of these materials as a suitable C source for the soil to promote long term soil C stabilisation.     

Application of compost of two-phase olive mill waste on olive grove: Effects on soil,olive fruit and olive oil quality

Composting is a method for preparing organic fertilizers that represents a suitable management option for the recycling of two-phase olive mill waste (TPOMW) in agriculture. Four different composts were prepared by mixing TPOMW with different agro-industrial by-products (olive pruning, sheep manure and horse manure), which were used either as bulking agents or as N sources. The mature composts were added during six consecutive years to a typical “Picual” olive tree grove in the Jaén province (Spain). The effects of compost addition on soil characteristics, crop yield and nutritional status and also the quality of the olive oil were evaluated at the end of the experiment and compared to a control treated only with mineral fertilization. The most important effects on soil characteristics included a significant increase in the availability of N, P, K and an increase of soil organic matter content. The application of TPOMW compost produced a significant increase in olive oil content in the fruit. The compost amended plots had a 15% higher olive oil content than those treatment with inorganic fertilization. These organics amendments maintained the composition and quality of the olive oil.     

Potential of olive mill wastes for soil C sequestration

The present work deals with the potential of olive mill wastes as a C source for soil C sequestration strategy, which is based on the high lignocellulosic content that makes these wastes to degrade slowly during composting and after land application. A C balance was performed during the whole life cycle of two different two-phase olive mill wastes (TPOMW): C losses were calculated during the composting process and after soil application of the composting mixtures under laboratory conditions. The effect of the degree of stabilization of TPOMW on the overall C waste conservation efficiency was also evaluated. C losses after 34 weeks of TPOMW composting ranged from 40.58% to 45.19% of the initial C, whereas the amount of C evolved as CO2 after 8 months of incubation of soil amended with mature composts only represented between 20.6% and 21.9% of the added C. The total C losses considering the whole life cycle of the TPOMW showed lower losses compared to composts prepared with organic residues of different origin. Conversely to the typical behaviour of other organic wastes, the stabilisation degree of the TPOMW composting mixtures did not show any significant effect on the total C losses measured during composting and later land application. The low rate of degradation of TPOMW both during composting and after soil application makes the use of TPOMW as a C source an attractive strategy for soil C sequestration.