Ambient levels of PFOS and PFOA in multiple environmental media

Making remediation and risk management decisions for widely‐distributed chemicals is a challenging aspect of contaminated site management. The objective of this study is to present an initial evaluation of the ubiquitous, ambient environmental distribution of poly‐ and perfluoroalkyl substances (PFAS) within the context of environmental decision‐making at contaminated sites. PFAS are anthropogenic contaminants of emerging concern with a wide variety of consumer and industrial sources and uses that result in multiple exposure routes for humans. The combination of widespread prevalence and low screening levels introduces considerable uncertainty and potential costs in the environmental management of PFAS. PFAS are not naturally‐occurring, but are frequently detected in environmental media independent of site‐specific (i.e., point source) contamination. Information was collected on background and ambient levels of two predominant PFAS, perfluorooctane sulfonate and perfluorooctanoate, in North America in both abiotic media (soil, sediment, surface water, and public drinking water supplies) and selected biotic media (human tissues, fish, and shellfish). The background or ambient information was compiled from multiple published sources, organized by medium and concentration ranges, and evaluated for geographical trends and, when available, also compared to health‐based screening levels. Data coverage and quality varied from wide‐ranging and well‐documented for soil, surface water, and serum data to more localized and less well‐documented for sediment and fish and shellfish tissues and some uncertainties in the data were noted. Widespread ambient soil and sediment concentrations were noted but were well below human health‐protective thresholds for direct contact exposures. Surface water, drinking water supply waters (representing a combination of groundwater and surface water), fish and shellfish tissue, and human serum levels ranged from less than to greater than available health‐based threshold values. This evaluation highlights the need for incorporating literature‐based or site‐specific background into PFAS site evaluation and decision‐making, so that source identification, risk management, and remediation goals are properly focused and to also inform general policy development for PFAS management.     

Speciation and Seasonal Variations of Dissolved Inorganic Arsenic in Jiaozhou Bay,North China

The distributions and biogeochemical cycles of arsenic in the aquatic environment have captured the interest of geochemists due to arsenic’s multiple chemical forms, the toxicity of certain arsenic species and large anthropogenic input. Seasonal variations in the dissolved inorganic arsenic concentration and speciation in Jiaozhou Bay, which is located on the west coast of the Yellow Sea in northern China, are presented here. Three cruises were carried out in Jiaozhou Bay under varying tidal regimes, one at neap tide and one at spring tide in August and one at spring tide in October of 2001. In addition to the transect surveys, the main sources of dissolved inorganic arsenate and arsenite in Jiaozhou Bay, including riverine input from five major tributary rivers, atmospheric dry and wet depositions, and groundwater and wastewater input, were collected in different seasons to estimate arsenic transport through different sources. The mean concentrations of total dissolved inorganic arsenic (TDIAs, As (V+III)) in Jiaozhou Bay were statistically comparable between summer and autumn, with higher concentrations at the northwest and northeast parts of the bay, reflecting human activities. The As (III)/TDIAs ratio ranged between 0.045 and 0.68, with an average of 0.16, implying that arsenate was the dominating species in Jiaozhou Bay. A preliminary box model was established to estimate the water-mass balance and arsenic budgets for Jiaozhou Bay, which demonstrated that river inputs and atmospheric depositions were the main sources of arsenic into Jiaozhou Bay. The concentrations of dissolved inorganic arsenic in Jiaozhou Bay have decreased in the last two decades. Compared with other areas in the world, the concentration of arsenic in Jiaozhou Bay remains at the natural level and this region can be characterized as a less disturbed area.     

Phytoremediation of arsenic‐contaminated soil as affected by the chelating agent CDTA and different levels of soil pH

Elevated levels of arsenic can pose a major threat to both human health and the environment. The phytoremediation of heavy metals from soil is emerging as a cost‐effective technology for the remediation of contaminated soils. The present greenhouse study was undertaken to identify plants capable of tolerating and accumulating high concentrations of arsenic. Asparagus fern and rye grass were found to tolerate and accumulate more than 1,100 ppm of arsenic in plant tissue. Arsenic uptake as affected by different levels of the chelating agent trans‐1, 2‐ cyclohexylenedinitrilotetraacetic acid (CDTA) and soil pH were also studied. The application of 5 mmol kg^?1 of CDTA to arsenic‐contaminated medium loam field soil enhanced the accumulation of arsenic by the test plants. Under these conditions, plants accumulated up to 1,400 ppm of arsenic as compared to 950 ppm by the plants grown in soil containing 1,200 ppm of arsenic but without any amendment of the chelating agent. Plants grown in field soil of pH 5 containing 300 ppm of arsenic absorbed higher concentrations of arsenic than at other tested pH levels. Corresponding reductions in arsenic content of soil after plant harvests were observed. © 2001 John Wiley & Sons, Inc.     

Arsenic and thallium data in environmental samples: Fact or fiction?

Matrix effects may increasingly lead to erroneous environmental decisions as regulatory limits or risk‐based concentrations of concern for trace metals move lower toward the limits of analytical detection. A U.S. Environmental Protection Agency Office of Technical Standards Alert estimated that environmental data reported using inductively coupled plasma spectrometry (ICP‐AES) has a false‐positive rate for thallium of 99.9 percent and for arsenic of 25 to 50 percent. Although this does not seem to be widely known in the environmental community, using three case studies, this article presents data in environmental samples that demonstrate severe matrix effects on the accuracy of arsenic and thallium results. Case Study 1 involves soil results with concentrations that approached or exceeded the applicable regulatory soil cleanup objectives of 13 mg/kg for arsenic and 2 mg/kg for thallium. Reanalysis using ICP coupled with a mass spectrometer (ICP‐MS) confirmed all thallium results were false positives and all arsenic results were biased high, concluding no action was required for soil remediation. Case Study 2 involves groundwater results for thallium at a Superfund site, where thallium was detected in groundwater up to 21.6 μ g/L using ICP‐AES. Reanalysis by ICP‐MS reported thallium as nondetect below the applicable regulatory level in all samples. ICP‐MS is usually a more definitive and accurate method of analysis compared to ICP‐AES; however, this is not always the case, as we demonstrate in Case Study 3, using data from groundwater samples at an industrial site. Through a weight‐of‐evidence approach, it is demonstrated that although method quality control results were acceptable, interferences in some groundwater samples caused biased high results for arsenic using ICP‐MS, which were significantly lower when reanalyzed using hydride generation atomic fluorescence spectrometry. Causes of these interference effects and conclusions from the three case studies to obtain accurate metal data for site assessment, risk characterization, and remedy selection are discussed. © 2010 Wiley Periodicals, Inc.     

Evaluation of soil-washing process for “unwashable” clays and silts from the palmerton zinc site

The Palmerton Zinc Site is a Superfund site in Palmerton, Pennsylvania. Its former mineral processing operations have contaminated nearby wells and soils with zinc and cadmium. Preliminary analysis of soil and dust sampling conducted in May 1991 has revealed that the dust poses a potential threat to human health. Based on the results of a previous study, which showed a high percentage of silt and clay in soils from Palmerton residential properties, it was concluded that soil washing is not likely to be a viable method to treat the soil and dust contamination in Palmerton. However, since the completion of this study, a soil-washing process for “unwashable” clays and silts has been developed. A residential soil sample from Palmerton, which had low concentrations of arsenic, cadmium, and lead, and a somewhat high concentration of zinc, was washed in a bench-scale version of this process. The results showed that the new soil-washing process for “unwashable” clays and silts may be a viable method to treat the soil and dust contamination in Palmerton, depending on the soil quality criteria concentrations selected for site cleanup.     

The GaNE programme in a global perspective

This paper provides the background to this special issue, outlining the extent to which the global atmospheric nitrogen cycle has been modified by human activity and outlining the range of effects. The global total emissions of reduced and oxidized nitrogen, amount to 124 Tg N, and exceed those from natural sources (34 Tg N) by almost a factor of four showing the extent to which anthropogenic activity has taken over the global N cycle. Of the 124 Tg N, 70 Tg N is emitted in the oxidized form, largely as NO and 70% of which results directly from anthropogenic activity. The remaining 54 Tg N is emitted as NH₃, (66% anthropogenic). The enhanced nitrogen emissions are associated with a range of local, regional and global issues including, acidification, eutrophication, climate change, human health and tropospheric O₃. The paper also places the Global Nitrogen Enrichment (GaNE) research programme in the UK in a wider perspective.     

The GaNE programme in a global perspective

This paper provides the background to this special issue, outlining the extent to which the global atmospheric nitrogen cycle has been modified by human activity and outlining the range of effects. The global total emissions of reduced and oxidized nitrogen, amount to 124 Tg N, and exceed those from natural sources (34 Tg N) by almost a factor of four showing the extent to which anthropogenic activity has taken over the global N cycle. Of the 124 Tg N, 70 Tg N is emitted in the oxidized form, largely as NO and 70% of which results directly from anthropogenic activity. The remaining 54 Tg N is emitted as NH₃, (66% anthropogenic). The enhanced nitrogen emissions are associated with a range of local, regional and global issues including, acidification, eutrophication, climate change, human health and tropospheric O₃. The paper also places the Global Nitrogen Enrichment (GaNE) research programme in the UK in a wider perspective.     

Reduced sulfur compounds in gas from construction and demolition debris landfills

The biological conversion of sulfate from disposed gypsum drywall to hydrogen sulfide (H(2)S) in the anaerobic environment of a landfill results in odor problems and possible health concerns at many disposal facilities. To examine the extent and magnitude of such emissions, landfill gas samples from wells, soil vapor samples from the interface of the waste and cover soil, and ambient air samples, were collected from 10 construction and demolition (C&D) debris landfills in Florida and analyzed for H(2)S and other reduced sulfur compounds (RSC). H(2)S was detected in the well gas and soil vapor at all 10 sites. The concentrations in the ambient air above the surface of the landfill were much lower than those observed in the soil vapor, and no direct correlation was observed between the two sampling locations. Methyl mercaptan and carbonyl sulfide were the most frequently observed other RSC, though they occurred at smaller concentrations than H(2)S. This research confirmed the presence of H(2)S at C&D debris landfills. High concentrations of H(2)S may be a concern for employees working on the landfill site. These results indicate that workers should use proper personal protection at C&D debris landfills when involved in excavation, landfill gas collection, or confined spaces. The results indicate that H(2)S is sufficiently diluted in the atmosphere to not commonly pose acute health impacts for these landfill workers in normal working conditions. H(2)S concentrations were extremely variable with measurements occurring over a very large range (from less than 3 ppbv to 12,000 ppmv in the soil vapor and from less than 3 ppbv to 50 ppmv in ambient air). Possible reasons for the large intra- and inter-site variability observed include waste and soil heterogeneities, impact of weather conditions, and different site management practices.     

Distributional Patterns of Arsenic Concentrations in Contaminant Plumes Offer Clues to the Source of Arsenic in Groundwater at Landfills

The distributional pattern of dissolved arsenic concentrations from landfill plumes can provide clues to the source of arsenic contamination. Under simple idealized conditions, arsenic concentrations along flow paths in aquifers proximal to a landfill will decrease under anthropogenic sources but potentially increase under in situ sources. This paper presents several conceptual distributional patterns of arsenic in groundwater based on the arsenic source under idealized conditions. An example of advanced subsurface mapping of dissolved arsenic with geophysical surveys, chemical monitoring, and redox fingerprinting is presented for a landfill site in New Hampshire with a complex flow pattern. Tools to assist in the mapping of arsenic in groundwater ultimately provide information on the source of contamination. Once an understanding of the arsenic contamination is achieved, appropriate remedial strategies can then be formulated. © 2013 Wiley Periodicals, Inc.*     

Mobilization of iron and arsenic from soil by construction and demolition debris landfill leachate

Column experiments were performed to examine (a) the potential for leachate from construction and demolition (C&D) debris landfills to mobilize naturally-occurring iron and arsenic from soils underlying such facilities and (b) the ability of crushed limestone to remove these aqueous phase pollutants. In duplicate columns, water was added to a 30-cm layer of synthetic C&D debris, with the resulting leachate serially passed through a 30-cm soil layer containing iron and arsenic and a 30-cm crushed limestone layer. This experiment was conducted for two different soil types (one high in iron (10,400mg/kg) and the second high in iron (5400mg/kg) and arsenic (70mg/kg)); also monitored were control columns for both soil types with water infiltration alone. Despite low iron concentrations in the simulated C&D debris leachate, elevated iron concentrations were observed when leachate passed through the soils; reductive dissolution was concluded to be the cause of iron mobilization. In the soil containing elevated arsenic, increased iron mobilization from the soil was accompanied by a similar but delayed arsenic mobilization. Since arsenic sorbs to oxidized iron soil minerals, reductive dissolution of these minerals results in arsenic mobilization. Crushed limestone significantly reduced iron (to values below the detection limit of 0.01mg/L in most cases); however, arsenic was not removed to any significant extent.     

Issues in monitoring hazardous chemicals in stormwater runoff/discharges from superfund and other hazardous chemical sites

Deficiencies in design and execution render stormwater‐runoff monitoring programs for many hazardous chemical sites inadequate for assessing the potential environmental quality and public health impacts of chemicals in the runoff. Two pervasive problems are the use of analytical methods that are inadequate for measuring certain hazardous chemicals at potentially hazardous concentrations, and the application of “criteria/standards” that are inappropriate for evaluating the environmental/public health impacts of chemicals. These concerns are most notable for carcinogens and chemicals that bioaccumulate in edible aquatic organisms, including arsenic, chromium, beryllium, mercury, dioxins, organochlorine pesticides (such as DDT), and polychlorinated biphenyls; unrecognized pollutants; and nanomaterials. In order to appropriately evaluate whether the runoff/discharge from a hazardous chemical site is a threat to human health, the analytical methods must be sufficiently sensitive in critical concentration ranges; sampling regimens need to be sufficiently rigorous to provide reliable characterization of the content of the runoff, receiving water, and, for bioaccumulatable chemicals, levels in edible organisms in receiving water. Proper sampling and analysis will then provide data to enable the appropriate criteria/standards to be applied. © 2010 Wiley Periodicals, Inc.     

Evaluation of bioaccessible arsenic in fly ash by an in vitro method and influence of particle-size fraction on arsenic distribution

A huge amount of fly ash is produced by coal-fired power plants every year in China and leads to increasing environmental problems associated with disposal and treatment. It will be very helpful for the study of management and disposal of solid waste to understand the bioaccessibility and environmental behaviors of arsenic in fly ash. In this paper, an in vitro physiologically-based extraction test was applied to estimate the solubility and bioaccessibility of arsenic in fly ash in the human gastrointestinal tract. The fly ash samples were sieved into different fractions with different particle sizes (100–60, 60–10, 10–2.5, <2.5 μm). The influence of particle size on both total and bioaccessible arsenic was also investigated. The results demonstrated that arsenic concentrations in fly ash were significantly correlated with particle size. The proportion of bioaccessible arsenic (gastric and intestinal arsenic) accounting for the total arsenic was in the range of 36–67 %. The statistic analysis indicated that total arsenic in fly ash was linearly correlated with bioaccessible arsenic. The results illustrated that bioaccessible arsenic was dominated by total arsenic.     

Pesticide Impact Rating Index – A Pesticide Risk Indicator for Water Quality

Pesticide users, natural resource managers, regulators, government agencies and many others are concerned about the off-site impact of pesticides on the environment. Systematic methods of the assessment of potential risk of pesticides to environmental components can serve as valuable tools in decision making and policy formulation. Simple risk indicators have been developed which cover a range of scenarios such as toxicity to organisms, health of farm workers, consumer health, and residues in harvested produce. The authors have developed a software package named Pesticide Impact Rating Index (PIRI) that outputs an improved pesticide risk indicator for water quality. PIRI is a standalone, user-friendly, platform-independent program. It can be used to (i) rank pesticides in terms of their relative pollution potential to groundwater or surface water, and (ii) to compare different land uses in a catchment or at a regional scale in terms of their relative impact on water quality. It is based on pesticides use; the pathway through which the pesticides are released to the water resources (drift, runoff, erosion, leaching) and the value of the water resources threatened. Each component is quantified using pesticide characteristics (including toxicity to organisms at different trophic levels, i.e. fish, daphnia, algae, etc.), environmental and site conditions (e.g. organic carbon content of soil, water input, slope of land, soil loss, recharge rate, depth of water table, etc.). This paper describes two case studies of the application of PIRI in Australia. The comparison of the risk assessment by PIRI on these revealed that PIRI correctly estimated the pollution potential of pesticides in greater than 80% of cases. A GIS version of PIRI is described in a companion paper in this volume. An erratum to this article is available at .     

Perchlorate: Sources,uses, and occurrences in the environment

Perchlorate contamination of groundwater and soil continues to be a hot topic in many sectors, including industry, the federal Departments of Defense and Energy, regulators, and the general public. This article presents information on what is currently known regarding perchlorate uses, known and suspected naturally occurring versus anthropogenic perchlorate sources, and past and present manufacturing locations. It provides the reader with a baseline as well as background information to facilitate an understanding of perchlorate in the environment for the ultimate purpose of remediation. The article is based on research conducted by the Interstate Technology Regulatory Council for a forthcoming, more substantial perchlorate overview document scheduled for publication later in 2005. The document will include an overview of the chemical and discussions of remediation techniques and methods of analysis. © 2005 Wiley Periodicals, Inc.     

Microbial Removal of Arsenic

Bangladesh is currently the subject of the world's largest mass arsenic poisoning in history. Groundwater throughout Bangladesh and West Bengal is contaminated with naturally occurring arsenic from the alluvial and deltaic sediments that form the region's aquifers. It has been estimated that 75 million people are at risk of developing health effects associated with the ingestion of arsenic. This project focuses on the use of microorganisms such as bacteria and algae to remove arsenic from water. Arsenic in the arsenite form was used in the studies. Experiments were conducted with a common alga and wastewater bacteria. A common green algae Scenedesmus abundans was used for determining arsenic uptake in batch experiments. Results of the experiments indicated that the algae biosorption could be modeled by the conventional Langmuir isotherm model. Algae morphology studies indicated that the algae cells were impacted due to the presence of arsenic as evidenced by clumping or loss of cell clusters. The wastewater bacteria also were capable of high percent of arsenic removal. Results indicate that microbial uptake of arsenic may be a viable method of pretreatment of arsenic contaminated water. However algae and sludge disposal would pose a problem and will have to be dealt with accordingly.     

Above- and below-ground methane fluxes and methanotrophic activity in a landfill-cover soil

Landfills are a major anthropogenic source of the greenhouse gas methane (CH(4)). However, much of the CH(4) produced during the anaerobic degradation of organic waste is consumed by methanotrophic microorganisms during passage through the landfill-cover soil. On a section of a closed landfill near Liestal, Switzerland, we performed experiments to compare CH(4) fluxes obtained by different methods at or above the cover-soil surface with below-ground fluxes, and to link methanotrophic activity to estimates of CH(4) ingress (loading) from the waste body at selected locations. Fluxes of CH(4) into or out of the cover soil were quantified by eddy-covariance and static flux-chamber measurements. In addition, CH(4) concentrations at the soil surface were monitored using a field-portable FID detector. Near-surface CH(4) fluxes and CH(4) loading were estimated from soil-gas concentration profiles in conjunction with radon measurements, and gas push-pull tests (GPPTs) were performed to quantify rates of microbial CH(4) oxidation. Eddy-covariance measurements yielded by far the largest and probably most representative estimates of overall CH(4) emissions from the test section (daily mean up to ～91,500μmolm(-2)d(-1)), whereas flux-chamber measurements and CH(4) concentration profiles indicated that at the majority of locations the cover soil was a net sink for atmospheric CH(4) (uptake up to -380μmolm(-2)d(-1)) during the experimental period. Methane concentration profiles also indicated strong variability in CH(4) loading over short distances in the cover soil, while potential methanotrophic activity derived from GPPTs was high (v(max)～13mmolL(-1)(soil air)h(-1)) at a location with substantial CH(4) loading. Our results provide a basis to assess spatial and temporal variability of CH(4) dynamics in the complex terrain of a landfill-cover soil.     

Regional material management and environmental protection

The goal of environmental protection is to prevent damage by early recognition of possible hazards. In the present paper, the potential of materials accounting techniques to forewarn of critical loadings on water, air and soil is assessed. For this purpose, the anthropogenic and natural contributions to the metabolism of a region are measured and estimated respectively. The control of man-made material fluxes to the environment is discussed with regard to a waste management concept based on sustainable fluxes of emissions and final storage quality of landfill materials. According to the results, regional material balances are powerful tools for integrated waste management: they allow the setting of priorities in waste management by identifying important material quantities and qualities, they are the base for the design and evaluation of waste treatment technologies, they are necessary for environmental impact statements, and they allow the recognition and minimization of the overall flux of materials from the anthroposphere to the environment.     

Health risk assessment of air emissions from a municipal solid waste incineration plant--a case study

A health risk assessment of long-term emissions of carcinogenic and non-carcinogenic air pollutants has been carried out for the municipal solid waste incinerator (MSWI) of the city of Taranto, Italy. Ground level air concentrations and soil deposition of carcinogenic (Polychlorinated Dibenzo-p-Dioxins/Furans and Cd) and non-carcinogenic (Pb and Hg) pollutants have been estimated using a well documented atmospheric dispersion model. Health risk values for air inhalation, dermal contact, soil and food ingestion have been calculated based on a combination of these concentrations and a matrix of environmental exposure factors. Exposure of the surrounding population has been addressed for different release scenarios based on four pollutants, four exposure pathways and two receptor groups (children and adults). Spatial risk distribution and cancer excess cases projected from plant emissions have been compared with background mortality records. Estimated results based on the MSWI emissions show: (1) individual risks well below maximum acceptable levels, (2) very small incremental cancer risk compared with background level.     

The application of ecological risk assessment principles to dispersant use planning

Ecological risk assessment is a formal process, either quantitative or semi-quantitative, to evaluate the possible ecological consequences of human activities and natural catastrophes. While formal risk assessments have been used for years when dealing with risks to human health, the application of such structured analyses is less common for environmental issues. It is, however, an area of intense interest, both scientifically and technically, in the United States at the present time. This paper suggests a methodology for applying ecological risk assessment protocols to the oil spill response planning process, which should improve our ability to compare and evaluate response options, especially controversial options such as the use of dispersants.     

Preliminary studies on potential remediation of acid mine drainage‐impacted soils by amendment with drinking‐water treatment residuals

Mining operations result in a wide range of environmental impacts: acid mine drainage (AMD) and acid sulfate soils being among the most common. Due to their acidic pH and high soluble metal concentrations, both AMD and acid sulfate soils can severely damage the local ecosystems. Proper post‐mining management practices are necessary to control AMD‐related environmental issues. Current AMD‐impacted soil treatment technologies are rather expensive and typically not environmentally sustainable. We conducted a 60‐day bench‐scale study to evaluate the potential of a cost‐effective and environment‐friendly technology in treating AMD‐impacted soils. The metal binding and acid‐neutralizing capacity of an industrial by‐product, drinking water treatment residuals (WTRs) were used for AMD remediation. Two types of locally generated WTRs, an aluminum‐based WTR (Al‐WTR) and a lime‐based WTR (Ca‐WTR) were used. Highly acidic AMD‐impacted soil containing very high concentrations of metals and metalloids, such as iron, nickel, and arsenic, was collected from the Tab‐Simco coal mine in Carbondale, Illinois. Soil amendment using a 1:1 Al‐ and Ca‐WTR mix, applied at 5 and 10 percent rates significantly lowered the soluble and exchangeable fractions of metals in the AMD‐impacted soil, thus lowering potential metal toxicity. Soil pH increased from an extremely acidic 2.69 to a near‐neutral 6.86 standard units over the 60‐day study period. Results from this preliminary study suggest the possibility of a successful scale‐up of this innovative, cost‐effective, and environmentally sustainable technology for remediating AMD‐impacted acid sulfate soils.