Critical Review of Environmental Forensic Techniques: Part II

A multitude of forensic techniques are available for age dating and source identification, including aerial photography interpretation, corrosion models, the commercial availability of a chemical, chemical associations with discrete types of equipment, chemical profiling, degradation models and contaminant transport models. The success of these techniques in environmental litigation and their applicability to a particular fact situation is rarely discussed in the literature. When these techniques are introduced as scientific evidence, their governing assumptions and the adequacy of the underlying data are rigorously scrutinized and often, successfully challenged. The purpose of this paper is to review selected forensic techniques and discuss their merits so that the user can select the technique or combination of techniques most appropriate for the factual elements of the case.     

Application of Forensic Techniques for Age Dating and Source Identification in Environmental Litigation

A multitude of forensic techniques are available for age dating and source identification, including corrosion models for underground storage tanks, the commercial availability of a compound, chemical associations with discrete types of manufacturing processes, chemical profiling, proprietary additives, stable isotope analysis, degradation models, biomarkers and contaminant transport models. The selection and use of these techniques in environmental litigation must be thoroughly understood and applied to be effective as forensic evidence. When introduced as scientific evidence, the governing assumptions and quality of the data are critically evaluated and frequently successfully challenged. The purpose of this paper is to present an overview of commonly used environmental forensic techniques and their possible applications so that a user can decide which technique or combination of methods is most appropriate for their case.     

Critical Review of Environmental Forensic Techniques: Part I

A multitude of forensic techniques are available for age dating and source identification, including aerial photography interpretation, corrosion models, the commercial availability of a compound, chemical associations with discrete type processes, chemical profiling, degradation models and contaminant transport models. These techniques, however, are rarely challenged or discussed in the literature relative to the scrutiny encountered in environmental litigation. When introduced as scientific evidence, the governing assumptions and quality of the data are critically evaluated and frequently successfully challenged. The purpose of this paper is to review five types of forensic techniques and discuss their merits so that a user can decide which technique, or combination of techniques, is most appropriate for developing the technical portion of a case.     

Critical Review of Environmental Forensic Techniques: Part I

A multitude of forensic techniques are available for age dating and source identification, including aerial photography interpretation, corrosion models, the commercial availability of a compound, chemical associations with discrete type processes, chemical profiling, degradation models and contaminant transport models. These techniques, however, are rarely challenged or discussed in the literature relative to the scrutiny encountered in environmental litigation. When introduced as scientific evidence, the governing assumptions and quality of the data are critically evaluated and frequently successfully challenged. The purpose of this paper is to review five types of forensic techniques and discuss their merits so that a user can decide which technique, or combination of techniques, is most appropriate for developing the technical portion of a case.     

Incorporating uncertainty in a chemical leaching assessment

Pesticide leaching models are being used to assist in the regulation and management of pesticides by indicating their potential for leaching to groundwater. Uncertainty in model input data is not, regrettably, included in most pesticide leaching assessments. In the work described here, we use logarithmic transformations of the attenuation factor (AF), a simple process-based index model, to represent uncertainty in a pesticide leaching assessment. Characterization of a wide range of pesticides as `leachers' or `non-leachers' for a specific Hawaii hydrogeological setting is facilitated by comparing the log-transformed AF, designated AFR, for each chemical with two reference chemicals for which leaching behavior in Hawaii is known. Defining a mean and uncertainty interval for the AFR index of each chemical being ranked provides a practical method of incorporating data uncertainty into a regulatory protocol.     

State of the Art Report on Multivariate Chemometric Methods in Environmental Forensics☆

Environmental forensic analysis has evolved significantly from the early days of qualitative chemical fingerprint evaluations. The need for quantitative rigor has made the use of numerical methods critical in identifying and mapping contaminant sources in complex environmental systems. Given multiple contaminant sources, the environmental scientist is faced with the challenge of unraveling the contributions of multiple plumes with overlapping spatial and temporal distributions. The problem may be addressed through a multivariate statistical approach, but there is a mind-boggling array of the available "chemometric" methods. This paper provides an overview of these methods, along with a review of their advantages, disadvantages, and pitfalls. Methods discussed include principal component analysis and several receptor-modeling techniques.     

State of the Art Report on Multivariate Chemometric Methods in Environmental Forensics

Environmental forensic analysis has evolved significantly from the early days of qualitative chemical fingerprint evaluations. The need for quantitative rigor has made the use of numerical methods critical in identifying and mapping contaminant sources in complex environmental systems. Given multiple contaminant sources, the environmental scientist is faced with the challenge of unraveling the contributions of multiple plumes with overlapping spatial and temporal distributions. The problem may be addressed through a multivariate statistical approach, but there is a mind-boggling array of the available “chemometric” methods. This paper provides an overview of these methods, along with a review of their advantages, disadvantages, and pitfalls. Methods discussed include principal component analysis and several receptor-modeling techniques.     

The ChimERA project: coupling mechanistic exposure and effect models into an integrated platform for ecological risk assessment

Current techniques for the ecological risk assessment of chemical substances are often criticised for their lack of environmental realism, ecological relevance and methodological accuracy. ChimERA is a 3-year project (2013–2016), funded by Cefic’s Long Range Initiative (LRI) that aims to address some of these concerns by developing and testing mechanistic fate and effect models, and coupling of these models into one integrated platform for risk assessment. This paper discusses the backdrop against which this project was initiated and lists its objectives and planned methodology.     

Speciation of zinc in contaminated soils

The chemical speciation of zinc in soil solutions is critical to the understanding of its bioavailability and potential toxic effects. We studied the speciation of Zn in soil solution extracts from 66 contaminated soils representative of a wide range of field conditions in both North America and Europe. Within this dataset, we evaluated the links among the dissolved concentrations of zinc and the speciation of Zn(2+), soil solution pH, total soil Zn, dissolved organic matter (DOM), soil organic matter (SOM) and the concentrations of different inorganic anions. The solid-liquid partitioning coefficient (K(d)) for Zn ranged from 17 to 13,100Lkg(-1) soil. The fraction of dissolved Zn bound to DOM varied from 60% to 98% and the soil solution free Zn(2+) varied from 40% to 60% of the labile Zn. Multiple regression equations to predict free Zn(2+), dissolved Zn and the solid-liquid partitioning of Zn are given for potential use in environmental fate modeling and risk assessment. The multiple regressions also highlight some of the most important soil properties controlling the solubility and chemical speciation of zinc in contaminated soils.     

Investigation,Remediation and Cost Allocation of Contaminants from the Britannia Mine in British Columbia: A Case Study

This case study, from the province of British Columbia, is described to illustrate the use of environmental forensic techniques. The study involves acid rock drainage (ARD) from the Britannia Mine, a mine located in southwestern British Columbia, that has been closed for approximately 25 years and discharges between 4 and 40 million litres of ARD, depending on the time of year into nearby Howe Sound every day. The ARD occurs as an oxidation of sulphide mineralization exposed to air and water. The sources of ARD contamination from this site are copper, aluminium, iron, zinc and manganese. Current copper concentrations discharging from the 4100 Portal Level range from 40 to 100 mg/L. Environmental forensic techniques are applied to describe the origin of the contaminant release, the timing of the release, the distribution of the contamination, finding the responsible parties and allocating remediation costs for cleanup. Other forensic techniques described include the use of geochemistry to determine contaminant degradation.     

Mass conservative,positive definite integrator for atmospheric chemical dynamics

Air quality models compute the transformation of species in the atmosphere undergoing chemical and physical changes. The numerical algorithms used to predict these transformations should obey mass conservation and positive definiteness properties. Among all physical phenomena, the chemical kinetics solver provides the greatest challenge to attain these two properties. In general, most chemical kinetics solvers are mass conservative but not positive definite. In this article, a new numerical algorithm for the computation of chemical kinetics is presented. The integrator is called Split Single Reaction Integrator (SSRI). It is both mass conservative and positive definite. It solves each chemical reaction exactly and uses operator splitting techniques (symmetric split) to combine them into the entire system.The method can be used within a host integrator to fix the negative concentrations while preserving the mass, or it can be used as a standalone integrator that guarantees positive definiteness and mass conservation. Numerical results show that the new integrator, used as a standalone integrator, is second order accurate and stable under large fixed time steps when other conventional integrators are unstable.     

Refining emission rate estimates using a coupled receptor–dispersion modeling approach

Receptor modeling techniques like chemical mass balance are used to attribute pollution levels at a point to different sources. Here we analyze the composition of particulate matter and use the source profiles of sources prevalent in a region to estimate quantitative source contributions. In dispersion modeling on the other hand the emission rates of various sources together with meteorological conditions are used to determine the concentrations levels at a point or in a region. The predictions using these two approaches are often inconsistent. In this work these differences are attributed to errors in emission inventory. Here an algorithm for coupling receptor and dispersion models is proposed to reduce the differences of the two predictions and determine the emission rates accurately. The proposed combined approach helps reconcile the differences arising when the two approaches are used in a stand-alone mode. This work is based on assuming that the models are perfect and uses a model-to-model comparison to illustrate the concept.     

Chemical leasing: cooperative business models for sustainable chemicals management. Summary of research projects commissioned by the Austrian Federal Ministry of Agriculture, Forestry, Environment and Water Management

- Sustainable chemistry - Section editors: Klaus Günter Steinhäuser, Steffi Richter, Petra Greiner, Jutta Penning, Michael AngrickBackground, Aim and Scope Chemicals play a vital role in the day-to-day life of industrialised societies. Their use is not restricted to the chemical enterprises per se, but is a crucial part of production processes in a lot of industrial sectors. Traditional instruments of environmental policy (such as bans, restrictions) can only deal with the most hazardous substances. The Johannesburg Implementation Plan of 2002 calls for more sustainable patterns of production and consumption, and sets the year of 2020 as a goal to use chemicals in a way that human health and the environment are not endangered. Political instruments should not only gather more knowledge about the properties of chemicals, but should also stimulate the environmentally sound use of chemicals. Existing business models should therefore be reviewed in relation to this strategic approach to encourage marketing options with respect to the environmental focus.Main Features Business models were examined for their effects on the consumption of chemicals and amount of waste emissions in relation to their economic potential. Different possibilities for cooperation of supplier, user and disposal companies were elaborated and examined with a view to the specific situation in Austria.Results and Discussion A range of cooperative models – summarised under the term ‘chemical leasing’ - was identified, which can contribute to a more efficient use of resources. 12 main possible application areas (cleaning, lubrication, paint stripping and others) have been identified in Austria. If chemical leasing models were applied in these areas, the amounts of chemicals currently used could be reduced by one third (53,000 tonnes per year). Cost reductions of up to 15 % can be expected.Conclusion The application of chemical leasing models can contribute considerably to achieving more sustainable and resource-efficient patterns of production. The Austrian Ministry for Environment has therefore decided to subsidise the further practical implementation of these new service-oriented business models. Pilot projects in 4 enterprises, which are supervised by consulting companies, are currently being carried out. Recommendation and Outlook The experiences of the pilot projects will serve as valuable building blocks for the wider use of chemical leasing models. Furthermore, the UNIDO Cleaner Production Centres have expressed their clear interest and will examine the possibility to use chemical leasing as a part of their Cleaner Production Programmes.     

Evaluation of the STP model: comparison of modelled and experimental results for ten polycyclic aromatic hydrocarbons (PAHs)

Screening level risk assessment models are used by many countries to assess the treatability of organic chemicals during the sewage treatment process, especially those that are new to commerce. The performance of one such model, the sewage treatment plant model, is evaluated in the current study by comparing model predictions with actual measurement data collected at various stages of a typical full-scale activated sludge type sewage treatment plant. A suite of ten polycyclic aromatic hydrocarbons (PAHs) with widely varying physico–chemical properties were monitored for the comparison. Model predicted removal efficiencies were in very good agreement with those measured for all ten PAHs. Observed chemical concentrations and their trends at various stages of the sewage treatment process were also well simulated by the model. Results also suggest that a reasonable first approximation estimate of a range for the biodegradation half-life needed for the model may be obtained by dividing reported aqueous biodegradation half-life by scaling factors of 50 and 150.     

Numerical modeling of humic colloid borne americium (III) migration in column experiments using the transport/speciation code K1D and the KICAM model

The humic colloid borne Am(III) transport was investigated in column experiments for Gorleben groundwater/sand systems. It was found that the interaction of Am with humic colloids is kinetically controlled, which strongly influences the migration behavior of Am(III). These kinetic effects have to be taken into account for transport/speciation modeling. The kinetically controlled availability model (KICAM) was developed to describe actinide sorption and transport in laboratory batch and column experiments. Application of the KICAM requires a chemical transport/speciation code, which simultaneously models both kinetically controlled processes and equilibrium reactions. Therefore, the code K1D was developed as a flexible research code that allows the inclusion of kinetic data in addition to transport features and chemical equilibrium. This paper presents the verification of K1D and its application to model column experiments investigating unimpeded humic colloid borne Am migration. Parmeters for reactive transport simulations were determined for a Gorleben groundwater system of high humic colloid concentration (GoHy 2227). A single set of parameters was used to model a series of column experiments. Model results correspond well to experimental data for the unretarded humic borne Am breakthrough.     

A new challenge—development of test systems for the infochemical effect

Background, aim, and scope

Many—if not all—organisms depend on so-called infochemicals, chemical substances in their surroundings which inform the receivers about their biotic and abiotic environment and which allow them to react adequately to these signals. Anthropogenic substances can interfere with this complex chemical communication system. This finding is called infochemical effect. So far, it is not known to what extent anthropogenic discharges act as infochemicals and influence life and reproduction of organisms in the environment because adequate testing methods to identify chemicals which show the infochemical effect and to quantify their effects have not been developed yet. The purpose of this article is to help and find suitable test designs.

Main features

Test systems used in basic research to elucidate the olfactory cascade and the communication of environmental organisms by infochemicals are plentiful. Some of them might be the basis for a quantified ecotoxicological analysis of the infochemical effect. In principle, test systems for the infochemical effect could be developed at each step of the chemosensory signal transduction and processing cascade.

Results

Experimental set-ups were compiled systematically under the aspect whether they might be usable for testing the infochemical effect of single chemicals in standardized quantifying laboratory experiments. For an appropriate ecotoxicological assessment of the infochemical effect, experimental studies of many disciplines, such as molecular biology, neurobiology, physiology, chemical ecology, and population dynamics, should be evaluated in detail before a decision can be made which test system, respectively which test battery, might be suited best. The test systems presented here are based on the knowledge of the genetic sequences for olfactory receptors, binding studies of odorants, signal transmission, and reactions of the receivers on the level of the organisms or the populations. The following basic approaches are conceivable to identify the role of an infochemical: binding studies to the odorant-binding protein or to the odorant receptor binding protein (e.g., by in situ hybridization and immunohistochemical studies), measurement of electrical signals of the receptor cells in the tissue (e.g., electroolfactograms, electroantennograms), registration of phenotypic changes (e.g., observation under the microscope), behavioral tests (e.g., in situ online biomonitoring, use of T-shaped olfactometers, tests of avoidance responses), measurement of population changes (e.g., cell density or turbidity measurements), and multispecies tests with observation of community structure and community function. The main focus of this study is on aquatic organisms.

Discussion

It is evident that the infochemical effect is a very complex sublethal endpoint, and it needs further studies with standardized quantitative methods to elucidate whether and to what extent the ecosystem is affected. The collection of approaches presented here is far from being complete but should serve as a point of depart for further experimental research.

Conclusions

This article is the first to compare various approaches for testing the infochemical effect. The development of a suitable test system will not be easy as there are a multitude of relevant chemicals, a multitude of relevant receptors, and a multitude of relevant reactions, and it must be expected that the effective concentrations are very low. The chemical communication is of utmost importance for the ecosystem and justifies great endeavors to find solutions to these technical problems.

Recommendations and perspectives

The infochemical effect is a new chapter in ecotoxicology. Will a new endpoint, the so-called infochemical effect, be required in addition to the actual standard test battery of Annex 5 to Commission Directive 92/69/EEC (EC 1992)? Finding the answer to this question is a big challenge that could be met by a comprehensive research project.     

Redistribution of free tropospheric chemical species over West Africa: radicals (OH and HO₂), peroxide (H₂O₂) and acids (HNO₃ and H₂SO₄)

The purpose of this paper is to study the redistribution of chemical species (OH, HO₂, H₂O₂, HNO₃ and H₂SO₄) over West Africa, where the cloud cover is ubiquitously present, and where deep convection often develops. In this area, because of these cloud systems, chemical species are redistributed by the ascending and descending flow, or leached if they are soluble. So, we carry out a mesoscale study using the Regional Atmospheric Modelling System (RAMS) coupled to a code of gas and aqueous chemistry (RAMS_Chemistry). It takes into account all processes under mesh. We examine several cases following the period (November and July), with inputs emissions (anthropogenic, biogenic and biomass burning). The radicals OH and HO₂ are an indicator of possibilities for chemical activity. They characterize the oxidizing power of the atmosphere and are very strong oxidants. The acids HNO₃ and H₂SO₄ are interesting in their transformation into nitrates and sulfates in precipitation. In November, when photochemistry is active during an event of biomass burning, concentrations of chemical species are higher than those of November in the absence of biomass burning. The concentrations of nitric acid double and sulfuric acid increases 70 times. In addition, the concentrations are even lower in July if there is a deep convection. Compared to measures of the African Monsoon Multidisciplinary Analysis (AMMA), the results and observations of radicals OH and HO₂ are the same order of magnitude. Emissions from biomass burning increase the concentrations of acid and peroxide, and a deep convection cloud allows the solubility and the washing out of species, reducing their concentration. Rainfalls play a major role in solubility and washing out acids, peroxides and radicals in this region.     

Mineralogical compositions of aquifer matrix as necessary initial conditions in reactive contaminant transport models

Mineralogical compositions and their spatial distributions are important initial conditions for reactive transport modeling. However, popular Kd-based "reactive" transport models only require contaminant concentrations in the pore fluids as initial conditions, and minerals implicitly represent infinite sources and sinks in these models. That situation results in a general neglect of mineralogical characterization in site investigations. This study uses a coupled multi-component reactive mass transport model to predict the natural attenuation of a ground water plume at a uranium mill tailings site in western USA. Numerous ground water geochemistry data are available at this site, but mineralogical data are sketchy. Even given the well-defined pore fluid chemistry, variations of secondary mineral species and mineral abundances in the aquifer resulted in significantly different modeling outcomes. Results show that the amount of calcite in the aquifer determines the distances of plume migration. The possible presence of jurbanite, an aluminum sulfate phase, can store acidity temporarily but cause more severe contamination on a later date. The surfaces of iron oxyhydroxides can store significant amounts of sulfate and protons and serve as a second source for prolonged contamination. These simulations under field conditions illustrate that mineralogical compositions are an essential requirement for accurate prediction of contaminant fate and transport.     

Direct-push geochemical profiling for assessment of inorganic chemical heterogeneity in aquifers

Discrete-depth sampling of inorganic groundwater chemistry is essential for a variety of site characterization activities. Although the mobility and rapid sampling capabilities of direct-push techniques have led to their widespread use for evaluating the distribution of organic contaminants, complementary methods for the characterization of spatial variations in geochemical conditions have not been developed. In this study, a direct-push-based approach for high-resolution inorganic chemical profiling was developed at a site where sharp chemical contrasts and iron-reducing conditions had previously been observed. Existing multilevel samplers (MLSs) that span a fining-upward alluvial sequence were used for comparison with the direct-push profiling. Chemical profiles obtained with a conventional direct-push exposed-screen sampler differed from those obtained with an adjacent MLS because of sampler reactivity and mixing with water from previous sampling levels. The sampler was modified by replacing steel sampling components with stainless-steel and heat-treated parts, and adding an adapter that prevents mixing. Profiles obtained with the modified approach were in excellent agreement with those obtained from an adjacent MLS for all constituents and parameters monitored (Cl, NO(3), Fe, Mn, DO, ORP, specific conductance and pH). Interpretations of site redox conditions based on field-measured parameters were supported by laboratory analysis of dissolved Fe. The discrete-depth capability of this approach allows inorganic chemical variations to be described at a level of detail that has rarely been possible. When combined with the mobility afforded by direct-push rigs and on-site methods of chemical analysis, the new approach is well suited for a variety of interactive site-characterization endeavors.