Diversity of Carbonyl Compounds in Biogas and Natural Gas Revealed Using High-Resolution Mass Spectrometry and Nontarget Analysis.

Airborne carbonyl compounds such as formaldehyde, acrolein, and methyl ethyl ketone have long been chemicals-of-concern in the environment due to their reactivity and their potential for negative health effects. Standard methods for determining carbonyls in air, which focus on a set of 15 or fewer compounds, involve derivatization to form nonvolatile hydrazones, which can readily be analyzed via liquid chromatography (LC) with ultraviolet detectors. Here, we apply a new LC-high-resolution mass spectrometry (HRMS) method to natural gas and a variety of upgraded biofuels to better assess their total carbonyl profile using the inherent selectivity of the standard sampling methodology and the selectivity and sensitivity of HRMS. The standard method accounted for only 64% of the total carbonyl content in natural gas and between 26 and 45% of the total carbonyl content in biogas sources, with the balance detected by the new LC/HRMS method. An additional 540 compounds with molecular formulas consistent with carbonyl compounds were detected compared to only 14 target compounds using the standard method. These results demonstrate that the established method dramatically under-reports both the total carbonyl load and the diversity of carbonyl species in natural gas and biogas samples.

Chemical and Toxicological Properties of Emissions from a Light-Duty Compressed Natural Gas Vehicle Fueled with Renewable Natural Gas.

Biogas consisting primarily of methane (CH4) and carbon dioxide (CO2) can be upgraded to a transportation fuel referred to as renewable natural gas (RNG) by removing CO2 and other impurities. RNG has energy content comparable to fossil compressed natural gas (CNG) but with lower life-cycle greenhouse gas (GHG) emissions. In this study, a light-duty cargo van was tested with CNG and two RNG blends on a chassis dynamometer in order to compare the toxicity of the resulting exhaust. Tests for reactive oxygen species (ROS), biomarker expressions (CYP1A1, IL8, COX-2), and mutagenicity (Ames) show that RNG exhaust has toxicity that is comparable or lower than CNG exhaust. Statistical analysis reveals associations between toxicity and tailpipe emissions of benzene, dibenzofuran, and dihydroperoxide dimethyl hexane (the last identification is considered tentative/uncertain). Further gas-phase toxicity may be associated with tailpipe emissions of formaldehyde, dimethyl sulfide, propene, and methyl ketene. CNG exhaust contained higher concentrations of these potentially toxic chemical constituents than RNG exhaust in all of the current tests. Photochemical aging of the vehicle exhaust did not alter these trends. These preliminary results suggest that RNG adoption may be a useful strategy to reduce the carbon intensity of transportation fuels without increasing the toxicity of the vehicle exhaust.

Composition and Toxicity of Biogas Produced from Different Feedstocks in California.

Biogas is a renewable energy source composed of methane, carbon dioxide, and other trace compounds produced from anaerobic digestion of organic matter. A variety of feedstocks can be combined with different digestion techniques that each yields biogas with different trace compositions. California is expanding biogas production systems to help meet greenhouse gas reduction goals. Here, we report the composition of six California biogas streams from three different feedstocks (dairy manure, food waste, and municipal solid waste). The chemical and biological composition of raw biogas is reported, and the toxicity of combusted biogas is tested under fresh and photochemically aged conditions. Results show that municipal waste biogas contained elevated levels of chemicals associated with volatile chemical products such as aromatic hydrocarbons, siloxanes, and certain halogenated hydrocarbons. Food waste biogas contained elevated levels of sulfur-containing compounds including hydrogen sulfide, mercaptans, and sulfur dioxide. Biogas produced from dairy manure generally had lower concentrations of trace chemicals, but the combustion products had slightly higher toxicity response compared to the other feedstocks. Atmospheric aging performed in a photochemical smog chamber did not strongly change the toxicity (oxidative capacity or mutagenicity) of biogas combustion exhaust.

Ultrafine Particle Emissions from Natural Gas, Biogas, and Biomethane Combustion.

Biogas and biomethane (=purified biogas) are major renewable fuels that play a pivotal role in the evolving global energy economy. Here, we measure ultrafine particle (UFP; Dp (particle diameter) < 100 nm) emissions from the combustion of biomethane and biogas produced from five different representative sources: two food waste digesters, two dairy waste digesters, and one landfill. Combustion exhaust for each of these sources is measured from one or more representative sectors including electricity generation, motor vehicles, and household use. Results show that UFP emissions are similar when using biomethane and natural gas with similar sulfur and siloxane content. Approximately 70% of UFPs emitted from water heaters and cooking stoves were semivolatile, but 30% of the UFPs were nonvolatile and did not evaporate even under extremely high dilution conditions. Photochemical aging of biomethane combustion exhaust and natural gas combustion exhaust produced similar amounts of secondary organic aerosol (SOA) formation. The results of the current study suggest that widespread adoption of biogas and biomethane as a substitute for natural gas will not significantly increase ambient concentrations of primary and secondary UFPs if advanced combustion technology is used and the sulfur and siloxane content is similar for biogas/biomethane and natural gas.

Prenatal mercury exposure, autism, and developmental delay, using pharmacokinetic combination of newborn blood concentrations and questionnaire data: a case control study.

BACKGROUND: Methylmercury (MeHg), known for well over a century as a neurotoxin in adults, has more recently been studied for potential detrimental effects during early brain development. While several studies have estimated mercury exposure, they usually rely on either a single biomarker or questionnaire data, each of which has limitations. The goal of this paper was to develop a toxicokinetic model that incorporates both biomarker and questionnaire data to estimate the cumulative exposure to MeHg through seafood consumption using data collected from the Childhood Autism Risks from Genetics and the Environment (CHARGE) study. METHODS: We utilized a previously described discrete-time model that estimates blood MeHg concentration given a piecewise-constant ingestion rate and single-compartment pharmacokinetics. We measured newborn bloodspot Hg concentrations and obtained information pertaining to maternal fish consumption using a questionnaire. Using MeHg concentration estimates from the toxicokinetic model, cumulative MeHg exposure was estimated in children with autism, children with developmental delay, and typically developing children. Median estimated cumulative MeHg was compared among diagnostic groups using the Kruskal-Wallis Test. Multinomial logistic regression models were constructed to assess the association between cumulative MeHg concentration and the risk of autism and developmental delay (vs. typical development). RESULTS: The estimated average MeHg concentration of for all fish species consumed by mothers was 42 ppb. Median cumulative MeHg over gestation was similar across diagnostic groups (p-values raged from 0.91 to 0.98). After adjusting for potential confounding, we found no association between cumulative MeHg exposure and the risk of autism (OR = 0.95, 95% CI: 0.95, 1.12) or developmental delay (OR = 1.00, 95% CI: 0.89, 1.13). CONCLUSIONS: The toxicokinetic model described in this paper yielded fish MeHg concentration estimates that are consistent with fish species containing lower levels of MeHg. Overall, cumulative MeHg exposure does not appear to detectably elevate the risk of autism or developmental delay. Based on the regression standard error for the association between ASD and TD, we would have reported statistical significance for an adjusted odds ratio of 1.09 or larger. This method can easily be extended to other epidemiologic studies in which there is a biomarker measurement and questionnaire data regarding exposure.

Prenatal and neonatal peripheral blood mercury levels and autism spectrum disorders.

BACKGROUND: Prenatal and early-life exposures to mercury have been hypothesized to be associated with increased risk of autism spectrum disorders (ASDs). OBJECTIVES: This study investigated the association between ASDs and levels of total mercury measured in maternal serum from mid-pregnancy and infant blood shortly after birth. METHODS: The study sample was drawn from the Early Markers for Autism (EMA) Study. Three groups of children who were born in Orange County, CA in 2000-2001 were identified: children with ASD (n=84), children with intellectual disability or developmental delay (DD) (n=49), and general population controls (GP) (n=159). Maternal serum specimens and newborn bloodspots were retrieved from the California Department of Public Health prenatal and newborn screening specimen archives. Blood mercury levels were measured in maternal serum samples using mass spectrometer and in infant bloodspots with a 213 nm laser. RESULTS: Maternal serum and infant blood mercury levels were significantly correlated among all study groups (all correlations >0.38, p<0.01). Adjusted logistic regression models showed no significant associations between ASD and log transformed mercury levels in maternal serum samples (ASD vs. GP: OR [95% CI]=0.96 [0.49-1.90]; ASD vs. DD: OR [95% CI]=2.56 [0.89-7.39]). Results for mercury levels in newborn blood samples were similar (ASD vs. GP: OR [95% CI]=1.18 [0.71-1.95]; ASD vs. DD: OR [95% CI]=1.96 [0.75-5.14]). CONCLUSIONS: Results indicate that levels of total mercury in serum collected from mothers during mid-pregnancy and from newborn bloodspots were not significantly associated with risk of ASD, though additional studies with greater sample size and covariate measurement are needed.

Provision of forensic healthcare services for police custodial settings in England, Wales and Northern Ireland: Current practice and implications for other services?

Provision of forensic healthcare services may affect patient safety and criminal justice outcomes. We reviewed models of delivery for services in police custody in terms of cost, types of healthcare professionals and their minimum required experience, training and qualification. Relevant information was requested under the Freedom of Information Act from all police services in England, Wales and Northern Ireland. Additional information was sought from the London Ambulance Service and the Metropolitan Police Service. A third of respondent police services refused to provide the requested information and only a small minority answered the questions in their entirety. Many police services cited excessive cost and commercial interests as reasons for not providing the information. A marked variation in models of forensic healthcare provision across police services which responded was identified. London Ambulance Service call-outs to Metropolitan Police Service custody suites for those arrested varied from 0% to 3.8%. There is substantial inconsistency and variability of information on forensic healthcare services in police custody. A standardised national dataset of all aspects of police custodial healthcare (irrespective of by whom such services are provided) should be established. We advise that the Association of Police & Crime Commissioners, College of Policing the National Police Chiefs' Council and NHS England Health and Justice engage on these matters and work with the Faculty of Forensic & Legal Medicine, the United Kingdom Association of Forensic Nurses and Paramedics, and the College of Paramedics to restart the transfer of all police custodial healthcare services to the National Health Service.

Mobile source and livestock feed contributions to regional ozone formation in Central California.

A three-dimensional air quality model with 8 km horizontal resolution was applied to estimate the summertime ozone (O(3)) production from mobile sources and fermented livestock feed in California's San Joaquin Valley (SJV) during years 2000, 2005, 2010, 2015, and 2020. Previous studies have estimated that animal feed emissions of volatile organic compounds (VOCs) have greater O(3) formation potential than mobile-source VOC emissions when averaging across the entire SJV. The higher spatial resolution in the current study shows that the proximity of oxides of nitrogen (NO(x)) and VOC emissions from mobile sources enhances their O(3) formation potential. Livestock feed VOC emissions contributed 3-4 ppb of peak O(3) (8-h average) in Tulare County and 1-2 ppb throughout the remainder of the SJV during the CCOS 2000 July-August episode. In total, livestock feed contributed ~3.5 tons of the ground level peak O(3) (8 h average) in the SJV region, and mobile VOC contributed ~12 tons in this episode. O(3) production from mobile sources is declining over time in response to emissions control plans that call for cleaner fuels and engines with advanced emissions controls. Projecting forward to the year 2020, mobile-source VOC emissions are predicted to produce ~3 tons of the ground level peak O(3)(8-h average) and livestock feed VOC emissions are predicted to contribute ~2.5 tons making these sources nearly equivalent.

Complaints against health care professionals providing police custodial and forensic medical/health care services in England, Wales and Northern Ireland - what do we know?

Awareness of the nature and frequency of complaints against health care professionals working in police custodial health care services could provide opportunities to improve patient safety. To explore this freedom of information requests were sent to police services in England, Wales and Northern Ireland, to professional regulatory bodies and to the Independent Office for Police Conduct. Eighty-seven percent of police services responded but only a minority provided complete responses, with data not being held, or not being held in an easily retrievable format, being provided as reasons. The nature and frequency of complaints were similar to a previous 2017 study, suggesting a failure to learn lessons from the investigation of complaints and implement change in clinical practice. No evidence of an accessible complaints handling and recording procedure was provided across the police services surveyed. Regulatory bodies provided some information on the nature of complaints made against doctors and nurses working in police custodial settings, but that for paramedics was unable to do so. It is recommended that the communication loop between police services, those bodies providing health care and forensic medical services and regulatory bodies needs to be closed. A common reporting system or the application of established complaints handling procedures and reporting structures, which could be achieved by transferring these services to the National Health Service, may enhance patient safety in police custody.

Quantification of the effects of organic and carbonate buffers on arsenate and phosphate adsorption on a goethite-based granular porous adsorbent.

Interest in the development of oxide-based materials for arsenate removal has led to a variety of experimental methods and conditions for determining arsenate adsorption isotherms, which hinders comparative evaluation of their adsorptive capacities. Here, we systematically investigate the effects of buffer (HEPES or carbonate), adsorbent dose, and solution pH on arsenate and phosphate adsorption isotherms for a previously well characterized goethite-based adsorbent (Bayoxide E33 (E33)). All adsorption isotherms obtained at different adsorbate/adsorbent concentrations were identical when 1 mM of HEPES (96 mg C/L) was used as a buffer. At low aqueous arsenate and phosphate concentration (∼1.3 µM), however, adsorption isotherms obtained using 10 mM of NaHCO(3) buffer, which is a reasonable carbonate concentration in groundwater, are significantly different from those obtained without buffer or with HEPES. The carbonate competitive effects were analyzed using the extended triple layer model (ETLM) with the adsorption equilibrium constant of carbonate calibrated using independent published carbonate adsorption data for pure goethite taking into consideration the different surface properties. The successful ETLM calculations of arsenate adsorption isotherms for E33 under various conditions allowed quantitative comparison of the arsenate adsorption capacity between E33 and other major adsorbents initially tested under varied experimental conditions in the literature.

Identification and quantitation of volatile organic compounds emitted from dairy silages and other feedstuffs.

High ground-level ozone continues to be an important human, animal, and plant health impediment in the United States and especially in California's San Joaquin Valley (SJV). According to California state and regional air quality agencies, dairies are one of the major sources of volatile organic compounds (VOCs) in the SJV. A number of recently conducted studies reported emissions data from different dairy sources. However, limited data are currently available for silage and otherfeed storages on dairies, which could potentially contribute to ozone formation. Because the impact of different VOCs on ozone formation varies significantly from one molecular species to another, detailed characterization of VOC emissions is essential to include all the important contributors to atmospheric chemistry and especially atmospheric reactivity. The present research study identifies and quantifies the VOCs emitted from various silages and other feedstuffs. Experiments were conducted in an environmental chamber under controlled conditions. Almost 80 VOCs were identified and quantified from corn (Zea mays L.), alfalfa (Medicago sativa L.),and cereal (wheat [Triticum aestivum L.] and oat [Avena sativava L.] grains) silages, total mixed ration (TMR), almond (Amygdalus communis L.) shells and hulls using gas chromatography-mass spectrometry and high performance liquid chromatography. The results revealed high concentrations of emitted alcohols and other oxygenated species. Lower concentrations of highly reactive alkenes and aldehydes were also detected. Additional quantitation and monitoring of these emissions are essential for assessment of and response to the specific needs of the regional air quality in the SJV.

Determination of volatile organic compound emissions and ozone formation from spraying solvent-based pesticides.

Large-scale agricultural activities have come under scrutiny for possible contributions to the emission of ozone precursors. The San Joaquin Valley (SJV) of California is an area with intense agricultural activity that exceeds the federal ozone standards for more than 30 to 40 d yr(-1) and the more stringent state standards for more than 100 d yr(-1). Pesticides are used widely in both agricultural and residential subregions of the SJV, but the largest use, by weight of "active ingredient," is in agriculture. The objective of the study was to determine the role of pesticide application on airborne volatile organic compounds (VOC) concentrations and ozone formation in the SJV. The ozone formation from the pesticide formulation sprayed on commercial orchards was studied using two transportable smog chambers at four application sites during the summers of 2007 and 2008. In addition to the direct measurements of ozone formation, airborne VOC concentrations were measured before and after pesticide spraying using canister and sorbent tube sampling techniques. Soil VOC concentrations were also measured to understand the distribution of VOCs between different environmental compartments. Numerous VOCs were detected in the air and soil samples throughout the experiment but higher molecular weight aromatic hydrocarbons were the primary compounds observed in elevated concentrations immediately after pesticide spraying. Measurements indicate that the ozone concentration formed by VOC downwind of the orchard may increase up to 15 ppb after pesticide application, with a return back to prespray levels after 1 to 2 d.

Factorial experimental designs for enhancement of concurrent poly(hydroxyalkanoate) production and brewery wastewater treatment.

The influence of four main process parameters--solids retention time (SRT), hydraulic retention time (HRT), anoxic-oxic cycling, and carbon-to-nitrogen ratio (C/N ratio)--on poly(hydroxyalkanoate) (PHA) production, while treating brewery wastewater, was studied. Two sets of two-level, three-factor experimental designs were implemented to (1) determine the effects and interactions among process parameters, (2) assess their significance to PHA production, and (3) approximate optimal operational conditions. The HRT and SRT were found to be the crucial operational parameters affecting PHA production. The highest PHA content of 55% (on a cell-weight basis) was produced at a 4-day HRT and 4-day SRT, whereas a maximum PHA concentration of 907 mg/L was obtained at a 2-day HRT and 12-day SRT. The effect of anoxic conditions on PHA production was insignificant. The C/N ratio played a more important role in the PHA concentration in the system than in the PHA content in the biomass.

Surface modification induced cuprous oxide nanoparticle toxicity to duckweed at sub-toxic metal concentrations.

Nanoparticle capping agents are critical for controlling the growth, oxidation state, and final particle size during aqueous synthesis. However, despite the known phytotoxicity of cetyltrimethylammonium bromide (CTAB) to plants, it is used to synthesize metal oxide nanoparticles of uniform size and with mesoporous structure. Among the few studies that have investigated how CTAB influences nanoparticle toxicity, CTAB has never been identified as the primary cause of nanoparticle toxicity in environmental systems; rather nanoparticle surface charge or morphology was identified as the driver of toxicity in environmentally relevant systems. In the current study, CTAB release from CTAB surface modified Cu2O nanoparticles (SM-Cu2O NPs) inhibited duckweed (Landoltia punctata) growth, even when administered at subtoxic Cu concentrations. Organic ligands, such as humic acid (HA) and ethylenediaminetetraacetic acid (EDTA), lessened growth inhibition associated with exposure to SM-Cu2O NPs, likely through electrostatic and hydrophobic interactions with CTAB. Such results highlight the need for a more holistic approach to nanoparticle surface modification and improved communication between toxicologists and synthetic chemists to develop green alternatives for nanoparticle synthesis.

Statistical analysis of trace contaminants measured in biogas.

Biogas is a renewable energy fuel that can be treated to increase purity so that the resulting "biomethane" can be injected into the natural gas pipeline grid. The trace contaminants in biogas and biomethane make up a small fraction of the total gas but they still have the potential to cause adverse health effects and pipeline corrosion. This study investigates the statistical distributions of 17 trace metals, six mercaptans, hydrogen sulfide, ammonia, and six additional trace organic compounds. Twelve of these 31 trace contaminants have been previously identified as constituents of concern based on their toxicity profiles and through health risk assessment studies. Untreated and treated samples of biogas were collected from 12 different biogas production facilities using diverse feedstocks throughout California. Results show that most biogas trace contaminants follow a single log-normal distribution or a bi-modal lognormal distribution depending on the type of production facility. Treatment of biogas demonstrates some removal for all trace contaminants, but four constituents of concern (copper, lead, hydrogen sulfide, and methyl mercaptan) are predicted to have a >1% probability of exceeding trigger levels even after common treatments. This finding suggests that enhanced monitoring may be warranted for these contaminants. Several trace metals and volatile organic compounds (VOCs) were found to have seasonal trends with greater concentrations in the summer and lower concentrations in the winter suggesting that seasonal variation should be considered in future monitoring plans.

Leachability of dissolved chromium in asphalt and concrete surfacing materials.

Leachate metal pollutant concentrations produced from different asphalt and concrete pavement surfacing materials were measured under controlled laboratory conditions. The results showed that, in general, the concentrations of most metal pollutants were below the reporting limits. However, dissolved chromium was detected in leachate from concrete (but not asphalt) specimens and more strongly in the early-time leachate samples. As the leaching continued, the concentration of Cr decreased to below or close to the reporting limit. The source of the chromium in concrete pavement was found to be cement. The concentration of total Cr produced from leachate of different cement coming from different sources that was purchased from retail distributors ranged from 124 to 641mug/L. This result indicates that the potential leachability of dissolved Cr from concrete pavement materials can be reduced through source control. The results also showed that the leachability of dissolved Cr in hardened pavement materials was substantially reduced. For example, the concentration of dissolved Cr measured in actual highway runoff was found to be much lower than the Cr concentration produced from leachate of both open and dense graded concrete pavement specimens under controlled laboratory study. It was concluded that pavement materials are not the source of pollutants of concern in roadway runoff; rather most pollutants in roadway surface runoff are generated from other road-use or land-use sources, or from (wet or dry) atmospheric deposition.

Historical trends of trace metals in a sediment core from a contaminated tidal salt marsh in San Francisco Bay.

Sedimentation of metals preserves historical records of contaminant input from local and regional sources, and measurement of metals in sediment cores can provide information for reconstruction of historical changes in regional water and sediment quality. Sediment core was collected from Stege Marsh located in central San Francisco Bay (California, USA) to investigate the historical input of trace metals. Aluminum-normalized enrichment factors indicate that inputs from anthropogenic sources were predominant over natural input for Ag, Cu, Pb, and Zn. Among these, lead was the most anthropogenically impacted metal with enrichment factors ranging from 32 to 108. Depth profiles and coefficients of variation show that As, Cd, and Se were also influenced by anthropogenic input. The levels of these anthropogenically impacted metals decline gradually towards the surface due to regulation of the use of leaded gasoline, municipal and industrial wastewater discharge control, and closure of point sources on the upland of Stege Marsh. Although trace metal contamination is expected to be continuously declining, the rates of decline have slowed down. For lead, it is estimated to take 44, 82, and 153 years to decrease to probable effects level (112 microg/g), the San Francisco Bay ambient surface sediment level (43.2 microg/g), and the local baseline levels (5 microg/g), respectively. Some metals in surface sediments (0-6 cm) are still higher than sediment quality guidelines such as the probable effects level. To further facilitate the recovery of sediment quality, more efficient management plans need to be developed and implemented to control trace metals from non-point sources such as stormwater runoff.

Microbial community composition and denitrifying enzyme activities in salt marsh sediments.

Denitrifying microbial communities and denitrification in salt marsh sediments may be affected by many factors, including environmental conditions, nutrient availability, and levels of pollutants. The objective of this study was to examine how microbial community composition and denitrification enzyme activities (DEA) at a California salt marsh with high nutrient loading vary with such factors. Sediments were sampled from three elevations, each with different inundation and vegetation patterns, across 12 stations representing various salinity and nutrient conditions. Analyses included determination of cell abundance, total and denitrifier community compositions (by terminal restriction fragment length polymorphism), DEA, nutrients, and eluted metals. Total bacterial (16S rRNA) and denitrifier (nirS) community compositions and DEA were analyzed for their relationships to environmental variables and metal concentrations via multivariate direct gradient and regression analyses, respectively. Community composition and DEA were highly variable within the dynamic salt marsh system, but each was strongly affected by elevation (i.e., degree of inundation) and carbon content as well as by selected metals. Carbon content was highly related to elevation, and the relationships between DEA and carbon content were found to be elevation specific when evaluated across the entire marsh. There were also lateral gradients in the marsh, as evidenced by an even stronger association between community composition and elevation for a marsh subsystem. Lastly, though correlated with similar environmental factors and selected metals, denitrifier community composition and function appeared uncoupled in the marsh.

The correlation of potassium content and moisture in bovine liver samples analyzed for trace mineral concentrations.

Beef cattle in the United States are often found to be deficient in essential trace minerals such as copper and zinc. Established reference ranges for mineral concentrations exist and usually designate a concentration as adequate, marginal, deficient, or excessive. This research investigates a new method of interpreting detected elemental concentrations in bovine liver that will add confidence to the final diagnosis. This is based on the hypothesis that a correlation exists between potassium concentration and moisture in a bovine liver sample. This relationship between potassium and moisture content enables the diagnostician to more accurately predict mineral concentrations and wet weight regardless of sample moisture loss. Correlations were found between potassium content and percentage of moisture in experimental samples, clinical biopsies, and a validation study, to a statistical significance of P < 0.001. Experimental samples had a correlation coefficient of R2 = 0.95 and the mathematical relationship y = 2513.2x(-1.0662). Clinical biopsies had a correlation of R2 = 0.83 and the mathematical relationship y = 2203.4x(-0.991). The validation study had a correlation of R2 = 0.55 and a mathematical relationship y = 2321.4x(-0.952). An exponent of -1 is predicted by conservation of potassium mass. These findings have practical significance in maintaining and improving cattle growth, health, reproduction, and food safety.

Size dependent elemental composition of road-associated particles.

Stormwater particles often provide transport for metals and other contaminants, however only larger particles are effectively removed by typical best management practices. Fine particles and their associated constituents are more likely to reach receiving waters; this merits further investigation regarding the metal contribution of fine (d(p)<10 microm) and very fine (d(p)<1.5 microm) particles. Road associated particles were collected by vacuuming a road surface and by collecting highway stormwater runoff. A cell sorter was employed to sort road associated particles into four size ranges: 0.1-0.3, 0.3-0.5, 0.5-1.0, and 1.0-1.5 microm. These very fine particles, along with six particle size ranges (total range <2-63 microm) separated using a settling column, were analyzed for Al, Mn, Fe, Cr, Ni, Cu, Zn, and Pb using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Enrichment factors (EFs), calculated using Al as a basis to represent crustal contributions, were similar for the vacuumed road dust and the stormwater runoff. Fe and Mn were minimally depleted (0.1x) or near unity for all size ranges (Fe EF range 0.01-3.7; Mn EF range 0.02-10.6). Cr, Ni, Cu, Zn, and Pb were moderately (10x) to considerably (>100x) enriched for most size ranges; these metals were most enriched in the very fine fractions (max EF ~ 4900 in Zn, 0.1-0.3 microm). Based on this preliminary study, a cell sorter is an acceptable means of fractionating aqueous particles of diameter 0.1-1.5 microm. In spite of their minimal relative mass contribution, the very fine particles are environmentally relevant due to their mobility and enrichment in potentially toxic metals.