Interactions between biological and abiotic pathways in the reduction of chlorinated solvents

While biologically mediated reductive dechlorination continues to be a significant focus of chlorinated solvent remediation, there has been an increased interest in abiotic reductive processes for the remediation of chlorinated solvents. In situ chemical reduction (ISCR) uses zero‐valent iron (ZVI)–based technologies, such as nanoscale iron and bimetallic ZVI, as well as naturally occurring reduced minerals incorporating dual‐valent iron (DVI), such as magnetite, green rust, and iron sulfides that are capable of dechlorinating solvents. A more recent area of development in ISCR has been in combining biological and abiotic processes. There are several ways in which biological and abiotic processes can be combined. First, the interaction between the two may be “causative.” For example, the Air Force Center for Engineering and the Environment's biogeochemical reductive dechlorination (BiRD) technology combines a mulch barrier with hematite and gypsum to create an iron‐sulfide‐based reducing zone. Biodegradation under sulfate‐reducing conditions produces sulfide that combines with the hematite to form iron sulfides. As such, the BiRD technology is “causative”; the biological processes create reducing minerals. The biological generation of other reducing minerals such as magnetite, siderite, and green rust is feasible and is, with magnetite, observed in nature at some petroleum sites. A second type of interaction between abiotic and biotic processes is “synergistic.” For example, biological processes can enhance the activity of reduced metals/minerals. This is the basis of the EHC® ISCR technologies, which combine ZVI with a (slowly) degradable carbon substrate. This combination rapidly creates buffered, strongly reducing conditions, which result in more complete solvent degradation (i.e., direct mineralization). The extent and level of reducing activity commonly observed are much greater when both the carbon substrate and the ZVI are present. When the carbon substrate is expended, the reducing activity due to ZVI alone is much less. The understanding of biogeochemical processes and their impact on abiotic processes is still developing. As that understanding develops, new and improved methods will be created to enhance volatile organic compound destruction. © 2009 Wiley Periodicals, Inc.     

The Use of Hypodermic Needles as Critical Orifices in Air Sampling

Hypodermic needles are useful as convenient low-cost critical orifices to control the flow rate in air sampling. Variations in flow rate were less than five per cent for 41 needle gauge-length combinations. To provide maximum accuracy, a simple calibration procedure is described. Needles may be reused more than six times, if protected. Types of protectors are described. Resistances of protector, collector, and prefilter combinations affect criticality at nine liters/min. Simple sampling devices using needles as orifices are described.     

QUALITY OF 1995 SPRING TOTAL DISSOLVED GAS DATA: COLUMBIA AND SNAKE RWERS1

ABSTRACT: The quality of the U.S. Army Corps of Engineers' (Corps) total dissolved gas (TDG) data base for the 1995 spring spill season was reviewed to determine the value of this information in real-time management decisions regarding river operations. We concluded that problems in transmitting, archiving, correcting and interpreting the records constitute significant sources of data anomalies that affect the accuracy and reliability of information necessary to manage spill and TDG in the Columbia and Snake rivers. The data base that was reviewed covers 25 selected Columbia and Snake river stations, and includes real-time TDG data needed to regulate spill operations to maintain gas levels within state water quality standards and to monitor effects on fish and aquatic life during the salmon migration season. A wide range of anomalies (daily averages missing or in error or based on incomplete records) was detected in more than one-third (37 percent) of the Corps' gas data base. Extreme anomalies (daily averages including errors and discontinuities for more than eight hours in a day) were found in 16 percent of the data base. The Fish Passage Center, also reviewed the Corps' data and reported an overall 33 percent incidence of anomalous days. Despite arriving at similar findings about the Corps' data base, we detected a 28 percent discrepancy in the type of data anomalies between our analyses. Real. time improvements in the quality of the dissolved gas data base are necessary to provide managers with a reliable product from this monitoring effort.     

The adsorption of short single-stranded DNA oligomers to mineral surfaces

We studied the adsorption of short single-stranded deoxyribonucleic acid (ssDNA) oligomers, of approximately 30 nucleotides (nt) in length, of varying sequence, adenine + guanine + cytosine (AGC) content, and propensity to form secondary structure, to equal surface area samples of olivine, pyrite, calcite, hematite, and rutile in 0.1 M NaCl, 0.05 M pH 8.1 KHCO₃ buffer. Although the mineral surfaces have widely varying points of zero charge, under these conditions they show remarkably similar adsorption of ssDNA regardless of oligomer characteristics. Mineral surfaces appear to accommodate ssDNA comparably, or ssDNA oligomers of this length are able to find binding sites of comparable strength and density due to their flexibility, despite the disparate surface properties of the different minerals. This may partially be due charge shielding by the ionic strength of the solutions tested, which are typical of many natural environments. These results may have some bearing on the adsorption and accumulation of biologically derived nucleic acids in sediments as well as the abiotic synthesis of nucleic acids before the origin of life.     

Preying on commercial fisheries and accumulating paralytic shellfish toxins: a dietary analysis of invasive Dosidicus gigas (Cephalopoda Ommastrephidae) stranded in Pacific Canada

In fall of 2009, several mass strandings of Humboldt squid (Dosidicus gigas) occurred on Vancouver Island (49°7′60N 125°54′0W). Morphological dissections coupled with DNA barcoding of stomach contents revealed Sardinops sagax (Pacific sardine) and Clupea pallasii (Pacific herring) as their primary prey. Plastic nurdles, fishing line, bull kelp, eelgrass, and a guillemot feather were also discovered. The primary prey, Pacific sardines and Pacific herring, are known to bioaccumulate paralytic shellfish toxins (PSTs); additionally, both PSTs and domoic acid (DA) have been implicated in other mass strandings. Therefore, stomach contents, and other tissues when possible, were tested for PSTs and DA. Testing revealed DA concentrations below regulatory guidance levels for human consumption, yet PSTs were well in excess. Though we cannot conclude that PSTs were the definitive cause of the strandings, our findings are the first report of PSTs in D. gigas.     

Biodegradation modelling of a dissolved gasoline plume applying independent laboratory and field parameters

Biodegradation of organic contaminants in groundwater is a microscale process which is often observed on scales of 100s of metres or larger. Unfortunately, there are no known equivalent parameters for characterizing the biodegradation process at the macroscale as there are, for example, in the case of hydrodynamic dispersion. Zero- and first-order degradation rates estimated at the laboratory scale by model fitting generally overpredict the rate of biodegradation when applied to the field scale because limited electron acceptor availability and microbial growth are not considered. On the other hand, field-estimated zero- and first-order rates are often not suitable for predicting plume development because they may oversimplify or neglect several key field scale processes, phenomena and characteristics. This study uses the numerical model BIO3D to link the laboratory and field scales by applying laboratory-derived Monod kinetic degradation parameters to simulate a dissolved gasoline field experiment at the Canadian Forces Base (CFB) Borden. All input parameters were derived from independent laboratory and field measurements or taken from the literature a priori to the simulations. The simulated results match the experimental results reasonably well without model calibration. A sensitivity analysis on the most uncertain input parameters showed only a minor influence on the simulation results. Furthermore, it is shown that the flow field, the amount of electron acceptor (oxygen) available, and the Monod kinetic parameters have a significant influence on the simulated results. It is concluded that laboratory-derived Monod kinetic parameters can adequately describe field scale degradation, provided all controlling factors are incorporated in the field scale model. These factors include advective–dispersive transport of multiple contaminants and electron acceptors and large-scale spatial heterogeneities.     

A spatial model of white sturgeon rearing habitat in the lower Columbia River,USA

Concerns over the potential effects of in-water placement of dredged materials prompted us to develop a GIS-based model that characterizes in a spatially explicit manner white sturgeon Acipenser transmontanus rearing habitat in the lower Columbia River, USA. The spatial model was developed using water depth, riverbed slope and roughness, fish positions collected in 2002, and Mahalanobis distance (D²). We created a habitat suitability map by identifying a Mahalanobis distance under which >50% of white sturgeon locations occurred in 2002 (i.e., high-probability habitat). White sturgeon preferred relatively moderate to high water depths, and low to moderate riverbed slope and roughness values. The eigenvectors indicated that riverbed slope and roughness were slightly more important than water depth, but all three variables were important. We estimated the impacts that fill might have on sturgeon habitat by simulating the addition of fill to the thalweg, in 3-m increments, and recomputing Mahalanobis distances. Channel filling simulations revealed that up to 9 m of fill would have little impact on high-probability habitat, but 12 and 15 m of fill resulted in habitat declines of ∼12% and ∼45%, respectively. This is the first spatially explicit predictive model of white sturgeon rearing habitat in the lower Columbia River, and the first to quantitatively predict the impacts of dredging operations on sturgeon habitat. Future research should consider whether water velocity improves the accuracy and specificity of the model, and to assess its applicability to other areas in the Columbia River.     

Air Quality Management in Los Angeles: Perspectives on Past and Future Emission Control Strategies

The 1988 Air Quality Management Plan was approved by the Board of the California South Coast Air Quality Management District in March 1989. The District comprises the counties of Los Angeles, Orange, and Riverside, and the non-desert portion of San Bernardino county. Emissions reductions in the past have lead to significant improvement in air quality despite large increases in growth. However, the District, largely because of continuous growth, currently violates the air quality standards for ozone, carbon monoxide, nitrogen dioxide, and respirable particulate matter (PM₁₀). Based upon the AQMP, reduction of approximately 80 percent in emissions of oxides of nitrogen and volatile organic compounds is required to bring the District into compliance with all air quality standards in the next twenty years.

Achieving compliance will necessitate the use of advanced technologies, as well as some changes in lifestyle and management practices. Advanced technologies, including the use of electric vehicles powered by batteries or fuel cells, the use of cleaner burning fuels and advanced combustion modifications, and treatment of surface coatings and solvents are included in the AQMP. The Technology Advancement Office in the District was created to work with industry, universities, research institutes, and other local, state and federal agencies to identify, evaluate, and promote low emitting fuels and technologies. In addition to electricity, fuels burning cleaner than conventional gasoline or diesel are being tested to obtain emissions and durability data so that rational choices can be made for the future. Compressed natural gas, methanol and liquefied petroleum gas are considered to be cleaner burning fuels for current applications. Ethanol, butane, and various oxygenated blends are being evaluated, and the broader application of solar energy and hydrogen are being investigated.

The impact of various cleaner burning fuels on air quality is being addressed. To date, methanol is the only fuel for which results are available. These results indicate that methanol use in vehicles—with control of formaldehyde emissions below 15 mg/mile for light-duty vehicles—can provide air quality benefits for all criteria pollutants and certain air toxics. These benefits are greater for M₁₀₀ than M₈₅.

Several District advanced technology programs are described, including a reduction in emissions from paints and coatings, and the demonstration of electric vehicles.     

Assessment of polybrominated diphenyl ethers in eggs of waterbirds from South China

Concentrations of total polybrominated diphenyl ethers (PBDEs) in Ardeid eggs from Hong Kong, Xiamen and Quanzhou in south China ranged from 140-1000, 30-550 and 140-380ngg(-1), lipid wt., respectively. There were spatial and interspecies variations in the abundance and congeneric profiles of PBDEs. The different congeneric profiles observed among the study sites may be associated with the developmental phases of the cities, as well as a possible consequence of debromination of BDE209. Marked concentrations of higher-brominated diphenyl ethers (BDEs 183, 196, 197, 206, 207 and 209) were detected in the egg samples from all sites, probably indicating uptake of BDE209 by top predators, and that there is widespread occurrence of BDE209 in south China. Comparisons of egg concentrations of BDEs 47, 99, 153 and 209 with tentative critical concentrations for neurobehavioral effects and oxidative stress indicated some potential risks for BDE99 and BDE209 in the Ardeid populations.     

Phosphorus transformations in plant-based and bio-waste materials induced by pyrolysis

Strategies are needed to increase the sustainability of phosphorus (P) fertiliser management in agriculture. This paper reports on the potential of pyrolysis treatment to recycle P from renewable materials previously regarded as wastes. The study used K-edge X-ray absorption near-edge structure (XANES) spectroscopy to examine chemical forms of P in the waste feedstock materials and corresponding biochars (pyrolysis at 480–500 °C) of four ligno-cellulosic, plant-based residues and five relatively P-rich livestock and water-treatment by-products, to acquire information on changes in potential P fertiliser value. Pyrolysis enriched P in the biochars by factors of 1.3–4.3, thus offering wide-ranging P fertiliser potential. XANES spectroscopy revealed hydroxyapatite (HAP) as one of the dominant chemical P compounds in the feedstocks, ranging from 14% (rice husks) to 98% (animal bone) of total P. For most materials, pyrolysis increased the proportion of HAP, and pyrophosphates were generated in several cases. These alterations possibly lead to diversity in the P solubility characteristics of the biochars if used as soil amendments; this is an important property of environmentally sound P fertilisers.