This document compares methods for extracting and quantifying water-transportable phenols from different land uses. Solid phase extraction (SPE) was used to extract dissolved organic matter from water samples collected from grassland, woodland, and moorland sites. SPE followed by thermally assisted hydrolysis and methylation with tetramethylammonium hydroxide (THM) was shown to be an effective approach for isolating and quantifying lignin-derived phenols. All the different land uses exported similar amounts of lignin per unit weight of organic carbon in the drainage water. A significant proportion of lignin phenols may be lost from soils in particulate form, so total phenol loss is likely greater than previously estimated from dissolved phenols
1) The study investigated how seasonal temperature changes affected the release of dissolved organic carbon (DOC) and phenols from soils treated with different plant litter types over 22 months.
2) The researchers found that seasonal soil temperature positively correlated with DOC loss from litter-free soils, but this correlation diminished over time for soils treated with grass and ash litter.
3) Phenol concentrations in the senescing litters were small, resulting in minor losses to water. The variety of dissolved phenols in litter-amended soil leachates increased over time and was influenced by litter type.
This document discusses using stable carbon isotope analysis to study phase transitions of soil carbonates during anaerobic biodegradation of petroleum hydrocarbons. It explains that carbonate minerals like calcite and dolomite are common in soils and can dissolve or form new minerals as conditions change. Stable carbon isotope ratios are measured to identify carbonate dissolution or addition. Laboratory experiments show that dissolving soil carbonates leads to re-formation of new carbonates during anaerobic degradation of hydrocarbons. This stable isotope method allows changes in the carbonate fraction of soil to be monitored.
Mineralization of Carbon from Sewage sludge in three soils of the Argentine p...Silvana Torri
Como citar este trabajo
Torri S, Alvarez R, Lavado R. 2003. Mineralization of Carbon from Sewage sludge in three soils of the Argentine pampas. Commun. Soil Sci. and Plant Anal. (Taylor & Francis, Inc., 325 Chestnut Street, Suite 800, Philadelphia, PA 19106) 34 (13-14): 2035-2043. ISSN (impresa): 0010-3624. ISSN (electronica): 1532-2416.
This document discusses geochemical controls during the biodegradation of petroleum hydrocarbons in soil. It provides background on past research showing microorganisms can use iron reduction to generate energy. More recent research has found biological iron redox transformations greatly influence aquifer and groundwater geochemistry. The document proposes a study to investigate intrinsic, iron-mediated degradation of volatile hydrocarbons like toluene in contaminated subsurface environments. It involves three stages: 1) laboratory experiments under anoxic conditions to simulate contaminated soil, 2) chemical extractions to assess iron pools involved in contaminant removal, and 3) stable carbon isotope analysis to differentiate carbonate pools and elucidate the effect of soil matrices on toluene removal and carbon
Assessment of fe(ii), fe(iii) and al(iii) in a mineralogical profile of gabon...Alexander Decker
1) The study assessed the fractions of Fe(II), Fe(III) and Al(III) in four depths of a Gabonese soil through water, KCl, and aqua regia extractions and analysis.
2) Total Fe(II) decreased with depth while total Al(III) and Fe(III) increased, with metals mainly in mineralogical fractions that decreased with depth.
3) This led to increases in water-soluble and exchangeable Fe(II) fractions and the exchangeable fractions of Al(III) and Fe(III) with depth, indicating increased solubility and mobility.
Evaluation of physicochemical properties of irrigated soilAlexander Decker
This document summarizes a study that evaluated the physical and chemical properties of soils from three irrigated farmlands along the bank of the Mada River in Nigeria. Soil samples were collected and various properties were measured, including moisture, pH, organic matter, cation exchange capacity, nitrogen, phosphorus, exchangeable cations, particle size and texture. The results found that soil properties varied between farms and most fell within suitable ranges for plant growth, though some nutrient levels were low. Correlations between pH, organic matter and cation exchange capacity were strongly positive. Overall, the soils were classified as sandy loamy.
Cation Concentrations of Anaocha, Ekwusigo And Ogbaru Local Government Areas ...IJRESJOURNAL
ABSTRACT: Soil samples collected from Anaocha, Ekwusigo and Ogbaru Local Government Areas of Anambra State were analyzed for their elemental compositions using Atomic Absorption Spectrophotometer. Physiochemical characteristics such as PH, particle size porosity, index/water holding capacity, moisture content and organic carbon were also analyzed. Results obtained from cation concentrations in mg/kg of the soils in Anaocha(A), Ekwusigo(E), and Ogbaru(O) were: K + (O>A>E); Na+ (O>A>E); Cr3+(A>E>O); Mg2+(O>A>E); Ni2+(E>A>O); Cu2+(O>E>A); Zn2+(E>A>O); Cd2+(O>A>E); Pb2+(O>A>E); Fe3+(E>O>A) and Al3+ (E>O>A). Other physiochemical characteristics showed that Anaocha soils were acidic, pH (5.13); Ekwusigo, pH (5.79) moderately acidic and Ogbaru pH (6.99),almost neutral. Anaocha area had less clay particles of (8.69c), Ogbaru (13.67c) and Ekwusigo (22.65c). Statictical studies revealed that Cd, Cu, Pb and iron oxides were significant factors in the incidence of erosion in Anaocha area.
1) The study investigated how seasonal temperature changes affected the release of dissolved organic carbon (DOC) and phenols from soils treated with different plant litter types over 22 months.
2) The researchers found that seasonal soil temperature positively correlated with DOC loss from litter-free soils, but this correlation diminished over time for soils treated with grass and ash litter.
3) Phenol concentrations in the senescing litters were small, resulting in minor losses to water. The variety of dissolved phenols in litter-amended soil leachates increased over time and was influenced by litter type.
This document discusses using stable carbon isotope analysis to study phase transitions of soil carbonates during anaerobic biodegradation of petroleum hydrocarbons. It explains that carbonate minerals like calcite and dolomite are common in soils and can dissolve or form new minerals as conditions change. Stable carbon isotope ratios are measured to identify carbonate dissolution or addition. Laboratory experiments show that dissolving soil carbonates leads to re-formation of new carbonates during anaerobic degradation of hydrocarbons. This stable isotope method allows changes in the carbonate fraction of soil to be monitored.
Mineralization of Carbon from Sewage sludge in three soils of the Argentine p...Silvana Torri
Como citar este trabajo
Torri S, Alvarez R, Lavado R. 2003. Mineralization of Carbon from Sewage sludge in three soils of the Argentine pampas. Commun. Soil Sci. and Plant Anal. (Taylor & Francis, Inc., 325 Chestnut Street, Suite 800, Philadelphia, PA 19106) 34 (13-14): 2035-2043. ISSN (impresa): 0010-3624. ISSN (electronica): 1532-2416.
This document discusses geochemical controls during the biodegradation of petroleum hydrocarbons in soil. It provides background on past research showing microorganisms can use iron reduction to generate energy. More recent research has found biological iron redox transformations greatly influence aquifer and groundwater geochemistry. The document proposes a study to investigate intrinsic, iron-mediated degradation of volatile hydrocarbons like toluene in contaminated subsurface environments. It involves three stages: 1) laboratory experiments under anoxic conditions to simulate contaminated soil, 2) chemical extractions to assess iron pools involved in contaminant removal, and 3) stable carbon isotope analysis to differentiate carbonate pools and elucidate the effect of soil matrices on toluene removal and carbon
Assessment of fe(ii), fe(iii) and al(iii) in a mineralogical profile of gabon...Alexander Decker
1) The study assessed the fractions of Fe(II), Fe(III) and Al(III) in four depths of a Gabonese soil through water, KCl, and aqua regia extractions and analysis.
2) Total Fe(II) decreased with depth while total Al(III) and Fe(III) increased, with metals mainly in mineralogical fractions that decreased with depth.
3) This led to increases in water-soluble and exchangeable Fe(II) fractions and the exchangeable fractions of Al(III) and Fe(III) with depth, indicating increased solubility and mobility.
Evaluation of physicochemical properties of irrigated soilAlexander Decker
This document summarizes a study that evaluated the physical and chemical properties of soils from three irrigated farmlands along the bank of the Mada River in Nigeria. Soil samples were collected and various properties were measured, including moisture, pH, organic matter, cation exchange capacity, nitrogen, phosphorus, exchangeable cations, particle size and texture. The results found that soil properties varied between farms and most fell within suitable ranges for plant growth, though some nutrient levels were low. Correlations between pH, organic matter and cation exchange capacity were strongly positive. Overall, the soils were classified as sandy loamy.
Cation Concentrations of Anaocha, Ekwusigo And Ogbaru Local Government Areas ...IJRESJOURNAL
ABSTRACT: Soil samples collected from Anaocha, Ekwusigo and Ogbaru Local Government Areas of Anambra State were analyzed for their elemental compositions using Atomic Absorption Spectrophotometer. Physiochemical characteristics such as PH, particle size porosity, index/water holding capacity, moisture content and organic carbon were also analyzed. Results obtained from cation concentrations in mg/kg of the soils in Anaocha(A), Ekwusigo(E), and Ogbaru(O) were: K + (O>A>E); Na+ (O>A>E); Cr3+(A>E>O); Mg2+(O>A>E); Ni2+(E>A>O); Cu2+(O>E>A); Zn2+(E>A>O); Cd2+(O>A>E); Pb2+(O>A>E); Fe3+(E>O>A) and Al3+ (E>O>A). Other physiochemical characteristics showed that Anaocha soils were acidic, pH (5.13); Ekwusigo, pH (5.79) moderately acidic and Ogbaru pH (6.99),almost neutral. Anaocha area had less clay particles of (8.69c), Ogbaru (13.67c) and Ekwusigo (22.65c). Statictical studies revealed that Cd, Cu, Pb and iron oxides were significant factors in the incidence of erosion in Anaocha area.
Heavy metals contamination at whitespots – conlig, newtownards, northern irel...Alexander Decker
This study investigated heavy metal contamination at an abandoned lead mine in Northern Ireland. Soil samples were collected from 7 vertical profiles down to 80cm depth and analyzed for moisture content, pH, minerals using XRD and PXRF spectrometry, and heavy metals using ICP-MS. The results showed elevated levels of lead and other heavy metals accumulated in the topsoil of some profiles, likely due to surface runoff transporting contaminated materials. The clay-rich and slightly alkaline soil composition helped immobilize some heavy metals while allowing limited leaching of others like zinc. The dispersion of contaminants occurred through both surface water flow transporting particles and lateral migration of contaminated spoil materials.
11.phosphorus speciation in drinking water treatment residualsAlexander Decker
This document summarizes a study that used X-ray absorption near-edge structure (XANES) spectroscopy to analyze the speciation of phosphorus (P) in soils amended with biosolids and drinking water treatment residuals (WTRs). Two incubation experiments were conducted, one using soils from Egypt and one using soils from the United States. In the Egyptian experiment, different application rates of WTRs and biosolids were added to soils and incubated for 60 days. In the US experiment, soils were amended with various rates of WTRs and biosolids and incubated for 30 days. XANES spectroscopy was then used to identify the chemical forms of P present in the amended soils. The results provided information on
The document presents Rosemary Orlu's PhD thesis which investigates the geochemical controls of hydrocarbon degradation in soils under iron-reducing conditions. A series of mesocosm experiments were conducted to examine the effects of soil type, iron mineral amendments, and carbon sources on the biodegradation of toluene. Statistical models were developed to predict toluene removal based on the experimental data using a mixed effects modeling approach.
A geochemical assessment of soils within oke ogun area, southwestern nigeriaAlexander Decker
This document summarizes a study that analyzed soil samples from Oke-Ogun area in southwestern Nigeria to investigate concentrations of major elements and trace metals.
Key findings include:
1. Soil samples showed elevated levels of Pb, Cr, V, Mn, and Co compared to underlying bedrock, indicating enrichment during weathering.
2. Statistical analysis revealed associations between Cu-Pb-Cd-Ni-Co and Zn-V.
3. Principal component analysis identified three factors associated with differing sources for trace metals in the soils.
This document discusses the effects of biochar on soil properties. It begins by introducing biochar as a carbon-rich material produced from biomass pyrolysis that can improve soil physical and chemical conditions. Biochar has properties like large surface area and micropores that can increase soil porosity, water holding capacity, and aggregate stability when applied as a soil amendment. The document then reviews literature on the origin of biochar from Terra Preta soils, the pyrolysis process used to produce it, and how biochar application can restore degraded soils by gradually releasing nutrients. Key biochar properties discussed include surface area, pores, stability, and ability to adsorb materials. The document concludes by summarizing research showing biochar can increase
11.[40 51]correlates in groundwater quality parameters and textural classes o...Alexander Decker
This document summarizes a study that investigated the physicochemical status of groundwater in Ekakpamre, Nigeria, a community located in the oil-rich Niger Delta region. 10 groundwater samples were collected from boreholes about 1 km apart and analyzed along with soil samples from around the boreholes. The study found that clay-rich soils appeared to influence certain groundwater quality parameters like dissolved oxygen, total petroleum hydrocarbons, and potassium levels. While groundwater quality was generally similar across sampling locations, levels of lead and cadmium exceeded regulatory limits for drinking water in some samples, posing a potential public health risk. Principal component analysis identified three components that accounted for 100% of the variability in the original water quality data
Environmental impact of biosolids land applicationSilvana Torri
Como citar este trabajo
Torri S, Cabrera M. 2017 Environmental impact of biosolids land application. In: Organic Waste: Management Strategies, Environmental Impact and Emerging Regulations, Editor: M Collins, Nova Science Publishers, Inc., Hauppauge, NY 11788, ISBN: 978-1-53610-936-8, 185-208, 226 pp
The Changing of Soil Reaction and Exchangeable Aluminum on two Different Soil...Agriculture Journal IJOEAR
The document summarizes a study on the effects of dolomite application on soil reaction and exchangeable aluminum in two different soil orders: Ultisols Kentrong and Inceptisols Jatinangor in Indonesia. Dolomite applications significantly increased soil pH and decreased exchangeable aluminum in Ultisols Kentrong. In Inceptisols Jatinangor, dolomite increased soil pH insignificantly and did not significantly affect exchangeable aluminum. The results indicate that liming effects differ between soil orders depending on their inherent acidity levels.
Downward movement of potentially toxic elements in biosolids amended soils,Silvana Torri
Como citar este trabajo
Torri S.I., Corrêa R.S. 2012. Downward movement of potentially toxic elements in biosolids amended soils, Special issue: Biosolids Soil Application: Agronomic and Environmental Implications, Applied and Environmental Soil Science (ISSN: 1687-7667), Volume 2012, Article ID 145724, 7 pages, doi:10.1155/2012/145724.
This document discusses using phosphate oxygen isotope ratios (δ18OP) to better understand phosphorus cycling in agricultural soils. It presents the goals of developing δ18OP as a tracer to identify the bioavailable P fraction in soils and track the long-term fate of externally applied P. It describes sample processing methods, measurement techniques, and initial findings showing transformation of fertilizer P into recalcitrant apatite P pools in agricultural soils. The document concludes that stable isotope labeling and tracking allows a deeper understanding of P sources, transfer, and transformations in natural environments.
IRJET- Impact of Organic Matter on Volatilization of Petroleum VOCs from ...IRJET Journal
This document summarizes a study on the impact of soil organic matter on the volatilization of petroleum BTX (benzene, toluene, and xylenes) compounds from soil columns. The study used columns packed with alluvial soil containing different levels of organic matter. Samples were taken from the columns over 28 days to analyze the weekly volatilization of the BTX compounds. The results showed that higher organic matter content led to lower volatilization rates, with up to 1.66 times lower for benzene in soils with 20% more organic matter. Organic matter enhances sorption of contaminants in soil, retaining more of the BTX compounds and reducing their volatility. The vapor
About the Interaction between water and Pb, Zn, Cu, Cd, Fe, Mn, Ba Mineralize...QUESTJOURNAL
ABSTRACT: One of the most important environmental concerns at mining sites is acid mine drainage (DAM), which is formed by the exposure sulfide minerals to air and water. The consequent production of sulfuric acid reduces the quality of water bodies and may allow the solubilization of potentially toxic metals such as Pb, Zn, Cu, Cd, Fe, Mn and Al. There is a range of laboratory procedures, classified as static and kinetic. Which have been used to understand the acidification and neutralization potencies of a rock through water/rock interaction process. These procedures seek to describe, quantify and predict the compositional changes of the solid and liquid phases in natural systems. The choice of techniques, methods, procedures and protocols requires the understanding of the problem to be solved or mitigated and is related to the specific geochemical and geological characteristics of the site to be analyzed. The elaboration of experimental procedures involves sampling strategies, selection of methodologies, (Accuracy, precision, sensitivity, speed, cost) and thus equipment and other necessary materials. This work presents the main static and kinetic procedures, highlighting its principles, advantages and limitations for selection and application in carbonate rocks rich in sulphide minerals. PH, Acid-Base Accounting and Net Acid Generation (NAG) are the static methods chosen. While the kinetic procedures chosen for the study of the natural enrichment of toxic metals in sulfate carbonate rocks is leaching columns, the Soxhlet system and reaction reactors. To provide more consistent drainage forecasts and hence better plans for the management of The results of different methods should be analyzed together.
Phosphorus speciation in drinking water treatment residualsAlexander Decker
This document summarizes a study that used X-ray absorption near-edge structure (XANES) spectroscopy to analyze the speciation of phosphorus (P) in soils amended with biosolids and drinking water treatment residuals (WTRs). Two incubation experiments were conducted, one using soils from Egypt and one using soils from the United States. The experiments involved amending the soils with varying rates of biosolids and WTRs and analyzing the resulting P species after incubation periods of 60 days and 30 days, respectively. The results from both experiments indicated that the dominant P species formed depended on the soil type and application rates of biosolids and WTRs.
Spatial Distribution Of Soil Organic Carbon and Total Nitrogen in a Grid Samp...IJSRED
This document analyzes the spatial variability of organic carbon and total nitrogen in soil samples collected from Kubani, Nigeria. 210 soil samples were collected at 3 meter intervals and analyzed for organic carbon and total nitrogen content. Results showed standard deviations ranged from 0.44 to 2.36, indicating variability. Semi-variograms showed the range of spatial dependence was 14 meters for organic carbon and 45 meters for total nitrogen, meaning samples within those distances had similar contents. Kriged contour maps were produced that showed similar positions. The maps and spatial structures can help inform better future sampling and management decisions.
This study assessed the influence of different sources of iron (III) on the bioremediation of toluene in contaminated soil under anaerobic conditions. The study hypothesized that indigenous soil microorganisms could couple the reduction of iron (III) to the oxidation of toluene, and that adding different sources of iron as terminal electron acceptors could increase both the rate and extent of toluene removal. The study used mesocosms containing live soil, various iron mineral amendments (naturally occurring hematite, goethite, magnetite or laboratory synthesized 2-line ferrihydrite and lepidocrocite), and river water spiked with toluene. Samples were taken serially to monitor changes
Three arrays of MacroRhizone pore water samplers were deployed at the abandoned Devon Great Consols mine site to investigate water-substrate interactions and potential environmental contamination. Samples were taken from three distinct tailings types - copper, tin, and arsenic tailings - deposited at different stages of the mine's history. Pore water compositions varied significantly between tailings types, with copper tailings highest in copper, aluminum, and manganese, tin tailings highest in tin but lowest in other metals, and arsenic tailings highest in arsenic, sodium, and strontium but lowest in copper. This suggests ongoing geochemical processes influence pore water compositions differently in each tailings type. SEM-EDX analysis showed
The International Journal of Engineering and Science (The IJES)theijes
The International Journal of Engineering & Science is aimed at providing a platform for researchers, engineers, scientists, or educators to publish their original research results, to exchange new ideas, to disseminate information in innovative designs, engineering experiences and technological skills. It is also the Journal's objective to promote engineering and technology education. All papers submitted to the Journal will be blind peer-reviewed. Only original articles will be published.
The papers for publication in The International Journal of Engineering& Science are selected through rigorous peer reviews to ensure originality, timeliness, relevance, and readability
Executive Summary of Biochar Research 1.12.2016 (version 1.0) (2).docx FinalMichael Maguire
Biochar is a charcoal-like material produced from biomass through pyrolysis that can sequester carbon and improve soil water retention. Research shows biochar can effectively sequester carbon through its stable molecular structure and persist in soils for hundreds of years depending on production conditions. Studies also indicate biochar increases soil water retention by improving soil organic matter content and surface area. Based on these benefits, the document estimates converting 5.5 million dead trees in California to biochar could sequester over 17 million metric tons of carbon, generating over $227 million in carbon offset credits.
Ancient Stones in Modern Contexts by Lillian SizemoreMusiva
This document discusses how ancient mosaic techniques are still used today but now address modern themes. It explains that mosaics still use geometric and figurative patterns to embellish architecture, but now depict contemporary subjects like pop culture icons, modern attire, and everyday foods. While respecting classical traditions of materials and techniques, modern mosaics reflect the present moment through depictions of current events, popular culture, urban landscapes, and political figures. Mosaics have become a fusion of past and present influences that serve as artistic expressions for all generations.
Heavy metals contamination at whitespots – conlig, newtownards, northern irel...Alexander Decker
This study investigated heavy metal contamination at an abandoned lead mine in Northern Ireland. Soil samples were collected from 7 vertical profiles down to 80cm depth and analyzed for moisture content, pH, minerals using XRD and PXRF spectrometry, and heavy metals using ICP-MS. The results showed elevated levels of lead and other heavy metals accumulated in the topsoil of some profiles, likely due to surface runoff transporting contaminated materials. The clay-rich and slightly alkaline soil composition helped immobilize some heavy metals while allowing limited leaching of others like zinc. The dispersion of contaminants occurred through both surface water flow transporting particles and lateral migration of contaminated spoil materials.
11.phosphorus speciation in drinking water treatment residualsAlexander Decker
This document summarizes a study that used X-ray absorption near-edge structure (XANES) spectroscopy to analyze the speciation of phosphorus (P) in soils amended with biosolids and drinking water treatment residuals (WTRs). Two incubation experiments were conducted, one using soils from Egypt and one using soils from the United States. In the Egyptian experiment, different application rates of WTRs and biosolids were added to soils and incubated for 60 days. In the US experiment, soils were amended with various rates of WTRs and biosolids and incubated for 30 days. XANES spectroscopy was then used to identify the chemical forms of P present in the amended soils. The results provided information on
The document presents Rosemary Orlu's PhD thesis which investigates the geochemical controls of hydrocarbon degradation in soils under iron-reducing conditions. A series of mesocosm experiments were conducted to examine the effects of soil type, iron mineral amendments, and carbon sources on the biodegradation of toluene. Statistical models were developed to predict toluene removal based on the experimental data using a mixed effects modeling approach.
A geochemical assessment of soils within oke ogun area, southwestern nigeriaAlexander Decker
This document summarizes a study that analyzed soil samples from Oke-Ogun area in southwestern Nigeria to investigate concentrations of major elements and trace metals.
Key findings include:
1. Soil samples showed elevated levels of Pb, Cr, V, Mn, and Co compared to underlying bedrock, indicating enrichment during weathering.
2. Statistical analysis revealed associations between Cu-Pb-Cd-Ni-Co and Zn-V.
3. Principal component analysis identified three factors associated with differing sources for trace metals in the soils.
This document discusses the effects of biochar on soil properties. It begins by introducing biochar as a carbon-rich material produced from biomass pyrolysis that can improve soil physical and chemical conditions. Biochar has properties like large surface area and micropores that can increase soil porosity, water holding capacity, and aggregate stability when applied as a soil amendment. The document then reviews literature on the origin of biochar from Terra Preta soils, the pyrolysis process used to produce it, and how biochar application can restore degraded soils by gradually releasing nutrients. Key biochar properties discussed include surface area, pores, stability, and ability to adsorb materials. The document concludes by summarizing research showing biochar can increase
11.[40 51]correlates in groundwater quality parameters and textural classes o...Alexander Decker
This document summarizes a study that investigated the physicochemical status of groundwater in Ekakpamre, Nigeria, a community located in the oil-rich Niger Delta region. 10 groundwater samples were collected from boreholes about 1 km apart and analyzed along with soil samples from around the boreholes. The study found that clay-rich soils appeared to influence certain groundwater quality parameters like dissolved oxygen, total petroleum hydrocarbons, and potassium levels. While groundwater quality was generally similar across sampling locations, levels of lead and cadmium exceeded regulatory limits for drinking water in some samples, posing a potential public health risk. Principal component analysis identified three components that accounted for 100% of the variability in the original water quality data
Environmental impact of biosolids land applicationSilvana Torri
Como citar este trabajo
Torri S, Cabrera M. 2017 Environmental impact of biosolids land application. In: Organic Waste: Management Strategies, Environmental Impact and Emerging Regulations, Editor: M Collins, Nova Science Publishers, Inc., Hauppauge, NY 11788, ISBN: 978-1-53610-936-8, 185-208, 226 pp
The Changing of Soil Reaction and Exchangeable Aluminum on two Different Soil...Agriculture Journal IJOEAR
The document summarizes a study on the effects of dolomite application on soil reaction and exchangeable aluminum in two different soil orders: Ultisols Kentrong and Inceptisols Jatinangor in Indonesia. Dolomite applications significantly increased soil pH and decreased exchangeable aluminum in Ultisols Kentrong. In Inceptisols Jatinangor, dolomite increased soil pH insignificantly and did not significantly affect exchangeable aluminum. The results indicate that liming effects differ between soil orders depending on their inherent acidity levels.
Downward movement of potentially toxic elements in biosolids amended soils,Silvana Torri
Como citar este trabajo
Torri S.I., Corrêa R.S. 2012. Downward movement of potentially toxic elements in biosolids amended soils, Special issue: Biosolids Soil Application: Agronomic and Environmental Implications, Applied and Environmental Soil Science (ISSN: 1687-7667), Volume 2012, Article ID 145724, 7 pages, doi:10.1155/2012/145724.
This document discusses using phosphate oxygen isotope ratios (δ18OP) to better understand phosphorus cycling in agricultural soils. It presents the goals of developing δ18OP as a tracer to identify the bioavailable P fraction in soils and track the long-term fate of externally applied P. It describes sample processing methods, measurement techniques, and initial findings showing transformation of fertilizer P into recalcitrant apatite P pools in agricultural soils. The document concludes that stable isotope labeling and tracking allows a deeper understanding of P sources, transfer, and transformations in natural environments.
IRJET- Impact of Organic Matter on Volatilization of Petroleum VOCs from ...IRJET Journal
This document summarizes a study on the impact of soil organic matter on the volatilization of petroleum BTX (benzene, toluene, and xylenes) compounds from soil columns. The study used columns packed with alluvial soil containing different levels of organic matter. Samples were taken from the columns over 28 days to analyze the weekly volatilization of the BTX compounds. The results showed that higher organic matter content led to lower volatilization rates, with up to 1.66 times lower for benzene in soils with 20% more organic matter. Organic matter enhances sorption of contaminants in soil, retaining more of the BTX compounds and reducing their volatility. The vapor
About the Interaction between water and Pb, Zn, Cu, Cd, Fe, Mn, Ba Mineralize...QUESTJOURNAL
ABSTRACT: One of the most important environmental concerns at mining sites is acid mine drainage (DAM), which is formed by the exposure sulfide minerals to air and water. The consequent production of sulfuric acid reduces the quality of water bodies and may allow the solubilization of potentially toxic metals such as Pb, Zn, Cu, Cd, Fe, Mn and Al. There is a range of laboratory procedures, classified as static and kinetic. Which have been used to understand the acidification and neutralization potencies of a rock through water/rock interaction process. These procedures seek to describe, quantify and predict the compositional changes of the solid and liquid phases in natural systems. The choice of techniques, methods, procedures and protocols requires the understanding of the problem to be solved or mitigated and is related to the specific geochemical and geological characteristics of the site to be analyzed. The elaboration of experimental procedures involves sampling strategies, selection of methodologies, (Accuracy, precision, sensitivity, speed, cost) and thus equipment and other necessary materials. This work presents the main static and kinetic procedures, highlighting its principles, advantages and limitations for selection and application in carbonate rocks rich in sulphide minerals. PH, Acid-Base Accounting and Net Acid Generation (NAG) are the static methods chosen. While the kinetic procedures chosen for the study of the natural enrichment of toxic metals in sulfate carbonate rocks is leaching columns, the Soxhlet system and reaction reactors. To provide more consistent drainage forecasts and hence better plans for the management of The results of different methods should be analyzed together.
Phosphorus speciation in drinking water treatment residualsAlexander Decker
This document summarizes a study that used X-ray absorption near-edge structure (XANES) spectroscopy to analyze the speciation of phosphorus (P) in soils amended with biosolids and drinking water treatment residuals (WTRs). Two incubation experiments were conducted, one using soils from Egypt and one using soils from the United States. The experiments involved amending the soils with varying rates of biosolids and WTRs and analyzing the resulting P species after incubation periods of 60 days and 30 days, respectively. The results from both experiments indicated that the dominant P species formed depended on the soil type and application rates of biosolids and WTRs.
Spatial Distribution Of Soil Organic Carbon and Total Nitrogen in a Grid Samp...IJSRED
This document analyzes the spatial variability of organic carbon and total nitrogen in soil samples collected from Kubani, Nigeria. 210 soil samples were collected at 3 meter intervals and analyzed for organic carbon and total nitrogen content. Results showed standard deviations ranged from 0.44 to 2.36, indicating variability. Semi-variograms showed the range of spatial dependence was 14 meters for organic carbon and 45 meters for total nitrogen, meaning samples within those distances had similar contents. Kriged contour maps were produced that showed similar positions. The maps and spatial structures can help inform better future sampling and management decisions.
This study assessed the influence of different sources of iron (III) on the bioremediation of toluene in contaminated soil under anaerobic conditions. The study hypothesized that indigenous soil microorganisms could couple the reduction of iron (III) to the oxidation of toluene, and that adding different sources of iron as terminal electron acceptors could increase both the rate and extent of toluene removal. The study used mesocosms containing live soil, various iron mineral amendments (naturally occurring hematite, goethite, magnetite or laboratory synthesized 2-line ferrihydrite and lepidocrocite), and river water spiked with toluene. Samples were taken serially to monitor changes
Three arrays of MacroRhizone pore water samplers were deployed at the abandoned Devon Great Consols mine site to investigate water-substrate interactions and potential environmental contamination. Samples were taken from three distinct tailings types - copper, tin, and arsenic tailings - deposited at different stages of the mine's history. Pore water compositions varied significantly between tailings types, with copper tailings highest in copper, aluminum, and manganese, tin tailings highest in tin but lowest in other metals, and arsenic tailings highest in arsenic, sodium, and strontium but lowest in copper. This suggests ongoing geochemical processes influence pore water compositions differently in each tailings type. SEM-EDX analysis showed
The International Journal of Engineering and Science (The IJES)theijes
The International Journal of Engineering & Science is aimed at providing a platform for researchers, engineers, scientists, or educators to publish their original research results, to exchange new ideas, to disseminate information in innovative designs, engineering experiences and technological skills. It is also the Journal's objective to promote engineering and technology education. All papers submitted to the Journal will be blind peer-reviewed. Only original articles will be published.
The papers for publication in The International Journal of Engineering& Science are selected through rigorous peer reviews to ensure originality, timeliness, relevance, and readability
Executive Summary of Biochar Research 1.12.2016 (version 1.0) (2).docx FinalMichael Maguire
Biochar is a charcoal-like material produced from biomass through pyrolysis that can sequester carbon and improve soil water retention. Research shows biochar can effectively sequester carbon through its stable molecular structure and persist in soils for hundreds of years depending on production conditions. Studies also indicate biochar increases soil water retention by improving soil organic matter content and surface area. Based on these benefits, the document estimates converting 5.5 million dead trees in California to biochar could sequester over 17 million metric tons of carbon, generating over $227 million in carbon offset credits.
Ancient Stones in Modern Contexts by Lillian SizemoreMusiva
This document discusses how ancient mosaic techniques are still used today but now address modern themes. It explains that mosaics still use geometric and figurative patterns to embellish architecture, but now depict contemporary subjects like pop culture icons, modern attire, and everyday foods. While respecting classical traditions of materials and techniques, modern mosaics reflect the present moment through depictions of current events, popular culture, urban landscapes, and political figures. Mosaics have become a fusion of past and present influences that serve as artistic expressions for all generations.
1) O autor argumenta que o impeachment de Dilma Rousseff não pode ser caracterizado como um golpe de estado, pois foi previsto pela Constituição Federal e seu rito foi definido pelo Supremo Tribunal Federal.
2) O PT usa a expressão "não vai ter golpe" para mobilizar suas bases contra o impeachment, porém ela não tem embasamento legal, já que o processo é constitucional.
3) Existe o risco de o PT e aliados reagirem de forma violenta ao impeachment, como já foi sugerido por Lula, o presidente da CUT e o
O COMBATE ÀS DESIGUALDADES SOCIAIS NO CAPITALISMO SEGUNDO MARX E PIKETTYFernando Alcoforado
ARTIGO DE FERNANDO ALCOFORADO PUBLICADO PELA REVISTA POLÍTICA DEMOCRÁTICA SOB O TÍTULO "O COMBATE ÀS DESIGUALDADES SOCIAIS NO CAPITALISMO SEGUNDO MARX E PIKETTY DISPONÍVEL NO WEBSITE <http: />
Caravaggio, the great italian painter of Early Baroque style,His life and his Style. How to " build a subject with Light and dark, Historical Background, the Counter Reformation and the need of propaganda
Los deportes de invierno son actividades deportivas practicadas sobre nieve o hielo e incluyen patinaje (artístico, de velocidad, en pista corta y sincronizado), descenso en trineo (bobsleigh, dogsled racing, luge y skeleton) y snowboard (half-pipe, boarder cross, freestyle y eslalon).
An archaeological site is any location where evidence of past human activity exists and can be investigated through archaeological methods. Sites range from those with no visible remains to still-in-use structures. Many of the sites mentioned in the document are ancient cities from important past civilizations, including Angkor Wat, Carthage, Chaco Canyon, Chan Chan, Copán, Delphi, Ephesus, Great Zimbabwe, Knossos, Leptis, Mesa Verde, Ming Tombs, Mohenjo-daro, Mycenae, Nazca Lines, Palenque, Pompeii, Roman Forum, Sphinx of Giza, Karnak Temple, Luxor Temple, Teotihuacan,
Auxilia o diretor de arte e o diretor de fotografia.
- Cenógrafo: Responsável pela decoração e ambientação dos
cenários.
- Figurinista: Cuida dos figurinos e vestuário dos atores.
- Maquiador: Responsável pela caracterização dos atores.
- Efeitos especiais: Cria efeitos visuais, pirotécnicos e
mecânicos.
- Designer gráfico: Cria identidade visual, logotipos, pacotes
gráficos.
- Ilustrador: Desenvolve ilustra
Tutorial para criação de formulario google docsAldean
Este documento fornece um tutorial passo-a-passo para criar uma avaliação online no Google Forms, incluindo como adicionar perguntas, escolher tipos de respostas, enviar o formulário por e-mail e visualizar os resultados.
Heavy metals and acid rain were applied over 4 years to a model forest ecosystem to study their effects on soil microbial communities. Microbial biomass, basal respiration, and hydrolase enzyme activities were reduced by heavy metal contamination, especially in combination with acid rain. Analysis of phospholipid fatty acids and genetic fingerprints showed that heavy metals altered the structure of bacterial communities over time. While soil pH and available heavy metal levels were similar between treatments with just heavy metals and those with both heavy metals and acid rain, the combined treatment had more drastic negative effects on the microbial community. This suggests that acid rain exacerbates the toxicity of heavy metals to soil microorganisms.
This document discusses the impacts of climate change on soil carbon dynamics. It begins with definitions of key terms like climate change and climatic extremes. It then outlines the different global carbon pools, with soils containing the third largest pool. The document discusses how climate change can impact the quantity and quality of soil organic carbon through changes in temperature, CO2, precipitation patterns, and climate extremes. It also examines potential carbon losses from soils under different climate change scenarios and considers approaches to mitigate these impacts through improved agricultural and land management practices.
Environ Sci Technol. 2007 Dec 15;41(24):8240-7.
Major structural components in freshwater dissolved organic matter.
Lam B, Baer A, Alaee M, Lefebvre B, Moser A, Williams A, Simpson AJ.
Department of Chemistry, University of Toronto Scarborough, Toronto, Ontario, Canada M1C 1A4.
Dissolved organic matter (DOM) contains a complex array of chemical components that are intimately linked to many environmental processes, including the global carbon cycle, and the fate and transport of chemical pollutants. Despite its importance, fundamental aspects, such as the structural components in DOM remain elusive, due in part to the molecular complexity of the material. Here, we utilize multidimensional nuclear magnetic resonance spectroscopy to demonstrate the major structural components in Lake Ontario DOM. These include carboxyl-rich alicyclic molecules (CRAM), heteropolysaccharides, and aromatic compounds, which are consistent with components recently identified in marine dissolved organic matter. In addition, long-range proton-carbon correlations are obtained for DOM, which support the existence of material derived from linear terpenoids (MDLT). It is tentatively suggested that the bulk of freshwater dissolved organic matter is aliphatic in nature, with CRAM derived from cyclic terpenoids, and MDLT derived from linear terpenoids. This is in agreement with previous reports which indicate terpenoids as major precursors of DOM. At this time it is not clear in Lake Ontario whether these precursors are of terrestrial or aquatic origin or whether transformations proceed via biological and/ or photochemical processes.
PMID: 18200846 [PubMed - indexed for MEDLINE]
Carbon sequestration through the use of biosolids in soils of the Pampas reg...Silvana Torri
Como citar este trabajo
Torri S, Lavado R. 2011. Carbon sequestration through the use of biosolids in soils of the Pampas region, Argentina. In: Environmental Management: Systems, Sustainability and Current Issues.Editor: H. C. Dupont, Nova Science Publishers, Inc., Hauppauge, NY 11788,ISBN: 978-1-61324-733-4.pag. 221-236, 336 p
Particle-size fractions-dependent extracellular enzyme activity in sediments ...GJESM Publication
The distribution of extracellular enzyme activities in particle-size fractions of sediments was investigated
in a subtropical mangrove ecosystem. Five enzymes involved in carbon (C), nitrogen (N), and phosphorus (P) cycling were analyzed in the sand, silt, and clay of sediments. Among these fractions, the highest activities of phenol oxidase (PHO), β-D-glucosidase (GLU), and N-acetyl-glucosiminidase (NAG) were found in sand, and greater than bulk sediments of both intertidal zone (IZ) and mangrove forest (MG). This result implied that sand fractions might protect selective enzymes through the adsorption without affecting their activities. Additionally, the enzyme-based resource allocation in various particle-size fractions demonstrated that nutrients availability varied with different particle-size
fractions and only sand fraction of MG with highest total C showed high N and P availability among fractions. Besides,
the analysis between elemental contents and enzyme activities in particle size fractions suggested that enzymes could monitor the changes of nutrients availability and be good indicators of ecosystem responses to environmental changes. Thus, these results provided a means to assess the availability of different nutrients (C, N, and P) during decomposition of sediment organic matter (SOM), and thus helping to better manage the subtropical mangrove ecosystems to sequester C into SOM.
This study examines whether salt marshes are at risk of becoming carbon sources rather than carbon sinks due to increased nitrogen loading from pollution. The researchers hypothesize that chronic nitrogen fertilization will 1) increase the quality of plant litter, making it more decomposable, and 2) increase decay rates due to greater nutrient availability for microbes. They test these hypotheses by analyzing soil quality and microbial activity in fertilized and unfertilized salt marsh plots using infrared spectroscopy and a bioavailability assay to measure carbon dioxide emissions from decomposition. Preliminary results suggest fertilization has increased litter decomposition and altered the belowground carbon cycle.
1) Soil microbes play an important role in global carbon and nitrogen cycles by driving processes like organic matter decomposition, nitrogen fixation, and methane/nitrous oxide emissions.
2) Changing environmental conditions due to climate change, like increased temperature and altered precipitation, can impact soil microbial communities and gene expression.
3) Horizontal gene transfer between soil microbes may be a natural adaptation strategy to environmental changes, allowing microbes to acquire new genes that help them survive. Studying this process of natural transformation could provide insights into molecular-level climate change adaptation.
DNAPL Remediation with ClO2_UV-published paperDarcy Bye
This study investigated the sorption of PAHs, PCBs, phenols, and BTEX hydrocarbons from groundwater onto a subsoil core sample. It also examined the destruction of these contaminants in ClO2/UV solution systems using methanol as the carrier solvent. Sorption experiments showed the contaminants formed S-type isotherms and could be modeled using the Freundlich equation. Off-site travel times for the contaminants in groundwater ranged from 145 to 80,817 years based on sorption. Treatment with ClO2/UV destroyed 76-98% of the contaminants and produced no dioxins or furans as byproducts, demonstrating this method's potential for remediating recal
Zander 2007 - Allochthonous DOC in floodplain riversAlek Zander
This research article explores using solid phase microextraction gas chromatography (SPME-GC) to fingerprint dissolved organic carbon (DOC) from various allochthonous sources in floodplain rivers. SPME-GC is a solventless extraction technique that can detect semi-volatile and volatile organic compounds in DOC at parts-per-trillion levels. The study examines DOC leachates from leaves, bark, grass, soil and algae collected from the Murrumbidgee River floodplain. Preliminary results found each source material produced complex chromatograms of over 100 compounds and hierarchical cluster analysis distinguished the chemical profiles between sources, indicating SPME-GC could identify source-specific markers for DOC.
This document summarizes a study that compared the nitrate removal rates, efficiencies, and potential for pollution swapping of different organic carbon media in laboratory denitrification bioreactors. The media tested included lodgepole pine woodchips, cardboard, lodgepole pine needles, barley straw, and a soil control. Results showed nitrate removal was consistently over 99% for all media. However, when considering pollution swapping through the production of other nitrogen species and leaching of contaminants, removal efficiencies ranged from 67% to 95%. Phosphorus releases from the bioreactors exceeded thresholds for eutrophication. Greenhouse gas emissions were dominated by carbon dioxide and methane, with little nitrous oxide. Compar
Chemostratigraphy is the study of chemical variations in rock sequences based on elemental or isotopic composition. It provides a useful tool for unconventional resource exploration. Some chemical signatures in rocks, like stable isotopes, can be used as accurate stratigraphic markers because they record global environmental changes over thousands of years. Common tools in chemostratigraphy include oxygen, carbon, and strontium isotope analysis, with strontium isotopes widely used for correlation due to long ocean residence times allowing identification of major shifts in the isotopic curve.
This document discusses the composition and properties of soil. It describes soil as having three phases: solid, liquid, and gas. The solid phase contains minerals like quartz and clay minerals. Clay minerals are important due to their large surface area and ability to adsorb ions. The liquid phase is the soil solution and contains dissolved organic and inorganic components. The gas phase in soil contains lower oxygen and higher carbon dioxide than the atmosphere due to plant and microbial respiration. Organic matter in soil originates from plants and microbes and influences soil properties. Phyllosilicate clay minerals are described as having a permanent negative charge that influences cation retention and swelling behavior.
This document summarizes recent advances in removing uranium from contaminated soils using chemical and biological techniques. It discusses soil washing using water or chemical additives to dissolve and extract uranium. Soil acidification and addition of chelating agents like citric acid were found to maximize uranium solubility and extraction. Sodium bicarbonate achieved 75-90% uranium removal efficiency from contaminated soils. The document reviews various chemical leaching solutions for uranium removal and their effectiveness.
The document summarizes research from a dissertation on microbial contributions to carbon and nutrient cycling across tropical landscapes. It finds that:
1) Soil carbon and nutrients decline rapidly with depth, while microbial biomass and activity also decline but metabolic activity per unit biomass remains similar or increases in deeper soils.
2) Soil organic matter chemistry differs between forest types near the surface but not with soil type, and alkyl carbon may be important for long-term tropical carbon storage.
3) Specific phosphatase enzyme activity is higher in deeper soils, suggesting microbes invest more in phosphorus acquisition under resource-limited conditions.
2011 de la fuente et al. water extract al heavy metal movilityGermán Tortosa
This document summarizes a study that examined the impact of fresh and composted solid olive husk and their water-soluble fractions on soil heavy metal fractionation, microbial biomass, and plant uptake. A pot experiment was conducted using a contaminated soil treated with fresh or composted olive husk, their water extracts, or an untreated control. The compost reduced metal availability and plant uptake, while fresh olive husk increased manganese bioavailability and caused phytotoxicity. The water extract from fresh olive husk also increased manganese solubility but did not affect plant uptake. The water extract from compost did not significantly impact heavy metal solubility. Composted olive husk therefore seems most suitable for bi
This document summarizes a field study that estimated the carbon pool of semi-evergreen forests in Dehradun, India. Soil, above ground biomass, and litter samples were taken from four sites: riverside, degraded, scrub forest, and dense forest. Carbon stocks varied between the sites and were highest in the dense forest, followed by scrub forest. The lowest carbon stocks were found in the riverside and degraded sites. The study aimed to quantify the carbon sequestration potential of the different forest types.
Spatial distribution and environmental geochemistry of zinc metal in water an...Javier Quesada Duque
This document summarizes a study on the spatial distribution and fractionation of zinc metal in water and bottom sediments of Lagoon Burullus in Egypt. Zinc concentrations were measured at 14 sites covering the lagoon. Zinc was fractionated into five fractions using sequential extractions. The average zinc concentration in bottom sediments was 189 μg/g, about three times the average for earth's crust. Most zinc was found in the residual fraction, followed by organic, exchangeable, carbonate, and Fe-Mn hydroxides fractions. Zinc concentrations in water ranged from 0.7-3.6 μg/L. Higher concentrations were found in areas receiving agricultural and industrial discharges, indicating anthropogenic pollution sources
1) Long-term monitoring has shown that total soil respiration is higher in urban forests compared to rural forests in Baltimore. This study aims to determine if differences in earthworm abundance explain the higher respiration levels.
2) Field measurements of soil respiration, moisture, biomass, organic matter, and earthworm abundance were taken at urban and rural forest sites. Earthworms were extracted using a mustard solution.
3) Preliminary results showed earthworm biomass was higher in urban sites, suggesting higher respiration in urban forests could be due to earthworm respiration and stimulation of root respiration by earthworms. Earthworm abundance varied with soil moisture.
The document discusses soil characterization and acidity status in pine plantation forests. It presents results of chemical analyses performed on soil samples from 5 pine plantations containing 22 forest compartments. The key findings are:
1) Soil samples showed high levels of organic carbon (3.7-10%) and generally highly acidic pH, indicating an acidic soil environment dominated by aluminum buffering.
2) Soil pH decreased with increasing forest stand age, with the most decline in the first 20 years of afforestation.
3) Exchangeable acidity levels were slightly higher than exchangeable aluminum, suggesting aluminum is the dominant form of acidity in these soils.
1. Comparison of extraction efficiencies for water-transportable phenols
from different land uses
Jonathan S. Williams a,b
, Jennifer A.J. Dungait b
, Roland Bol b,c
, Geoffrey D. Abbott a,⇑
a
School of Civil Engineering and Geosciences, Drummond Building, Newcastle University, Newcastle upon Tyne NE1 7RU, UK
b
Department of Sustainable Soils and Grassland Systems, Rothamsted Research, North Wyke, Okehampton, Devon EX20 2SB, UK
c
Institute of Bio- and Geosciences, IBG-3: Agrosphere, Forschungszentrum Jülich, Germany
a r t i c l e i n f o
Article history:
Received 25 January 2016
Received in revised form 20 September
2016
Accepted 23 September 2016
Available online 1 October 2016
Keywords:
Dissolved organic matter
Phenols
Solid phase extraction
Tetramethylammonium hydroxide
Land use
a b s t r a c t
The composition and quantification of vascular plant-derived phenols in dissolved organic matter (DOM)
is of importance in understanding and estimating carbon flux from soils under different land uses. Solid
phase extraction (SPE) was used to extract waterborne organic matter (WBM), and thermally assisted
hydrolysis (THM) using tetramethylammonium hydroxide (TMAH) was compared with gas
chromatography-flame ionization detection (GC-FID) for the quantification of oxygenated aromatics in
WBM, from freshwater samples from grazed grassland, woodland and moorland land uses in southwest
England, UK.
WBM recovered with SPE correlated with water total organic carbon (TOC) content. SPE followed by
THM was shown to be the approach for isolating and quantifying water-transportable phenols. All the
different land uses exported similar amounts of lignin per unit weight of OC to the drainage water. We
also conclude that a significant proportion of lignin phenols is lost from soils as a component of WBM
in a particulate form, so the magnitude of total phenol loss is likely greater than previously thought.
Ó 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://
creativecommons.org/licenses/by/4.0/).
1. Introduction
Dissolved organic matter (DOM) represents an important frac-
tion of organic carbon (OC) since it is the most mobile fraction,
affecting many biogeochemical cycles in terrestrial and aquatic
environments (Bolan et al., 2011). The recent intensification of
the hydrological cycle with changing climate (Durack et al.,
2012) emphasizes the need to characterise the molecular composi-
tion of DOM in different land uses. Riverine dissolved OC (DOC)
concentration varies from ca. 1 mg/l in alpine environments
(Meybeck, 1982) to 25 mg/l for rivers draining swampy areas, e.g.
the Satilla River, Georgia (Berner and Berner, 2012), influenced
by climate variables, such as a wide annual mean temperature
with sufficient precipitation (Tian et al., 2013). The worldwide
average of 5.75 mg/l (Meybeck, 1982) equates to a flux of
0.25 Â 1015
g riverine DOC/yr transported to the ocean (Hedges
et al., 1997). The most important sources of DOM in soils are
decomposed plant litter, root exudates and microbial biomass
(Kalbitz et al., 2000), comprising, amongst others, lignin-derived
phenols, carbohydrate-derived compounds, n-alkanoic acids,
n-alkanes and smaller amounts of N-containing compounds such
as amino acids (Frazier et al., 2003, 2005; Bowen et al., 2009).
In soils, there is evidence that lignin phenols protect soil OM
(SOM) from oxidation, contributing to the antioxidant capacity of
soils, by scavenging reactive free radicals, thereby terminating
the oxidative chain reaction (Rimmer, 2006; Rimmer and Abbott,
2011). Aromatics in DOM, such as lignin-derived compounds, can
be preferentially stabilized by sorption to soil minerals, thereby
contributing to stable forms of SOM, compared with more labile
components such as carbohydrates (Kalbitz et al., 2005). This is
supported by the observation of decreasing dissolved lignin phe-
nols concentration with increasing depth in mineral soils in forest
ecosystems, attributed to their sorption to the soil matrix
(Guggenberger and Zech, 1994). However, fractionation of phenols
can arise where more oxidised (carboxylated) phenols tend to
remain in soil solution (Guggenberger and Zech, 1994), also
observed in their preferential dissolution in leachates directly from
plant litter (Hernes et al., 2007). Hedges and Parker (1976) pro-
posed a parameter for the total amount of lignin phenols in a sed-
iment (K) by summing the weights of phenols equivalent to S (S4,
S5 and S6) and G (G4, G5 and G6) moieties normalised to OC. This
was later corrected to take into account the input of cinnamyl phe-
nols (G18 and P18) to the sedimentary OM (Hedges and Mann,
1979b). Reported total dissolved lignin phenol concentration from
http://dx.doi.org/10.1016/j.orggeochem.2016.09.010
0146-6380/Ó 2016 The Authors. Published by Elsevier Ltd.
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
⇑ Corresponding author.
E-mail address: geoff.abbott@newcastle.ac.uk (G.D. Abbott).
Organic Geochemistry 102 (2016) 45–51
Contents lists available at ScienceDirect
Organic Geochemistry
journal homepage: www.elsevier.com/locate/orggeochem
2. the USA ranges from 0.07 mg/100 mg OC in island drains from the
Sacramento-San Joaquin River Delta (Eckard et al., 2007) to
8.13 mg/100 mg OC (for the 1000 Da–0.2 lm DOC fraction) for
the Big Pine Creek watershed (Dalzell et al., 2005), determined
from CuO oxidation. Assuming an average dissolved lignin phenol
concentration of 2.65 mg/100 mg OC (the mean of published river-
ine values; Ertel et al., 1986; Benner and Opsahl, 2001; Frazier
et al., 2003; Dalzell et al., 2005; Eckard et al., 2007), this amounts
to a riverine flux of 6.61 Â 1012
g dissolved lignin phenols/yr,
which clearly represents a substantial loss of terrestrial C in the
form of lignin. In addition to the large losses of dissolved lignin
phenols, the molecular structure of lignin monomers is unique to
vascular plants (Hedges and Mann, 1979a), allowing them to be
used as terrestrial biomarkers in aquatic ecosystems (Gardner
and Menzel, 1974; Goni et al., 1997).
Solid phase extraction (SPE) has been widely used to isolate
DOC from aqueous solutions (Aiken et al., 1979; Meyersschulte
and Hedges, 1986; Moran et al., 1991; Lara and Thomas, 1994;
Simpson, 2000; Wang et al., 2012). Comparison of hydrophobic
sorbents (C2, C8, C18, cyclohexyl and phenyl XAD-2) and ultrafiltra-
tion to extract marine humic substances, found that C18 achieved
the greatest extraction efficiency (Amador et al., 1990). Compar-
ison of different solid phase ‘‘sorbents” silica-based octadecyl
bonded phases (C18, C18EWP and C18OH), silica-based octyl bonded
phase (C8) and modified styrene divinyl benzene polymers (PPL
and ENV) – on surface seawater samples from the north Brazilian
shelf off the Maracaçumé Estuary showed that PPL achieved the
highest extraction efficiency for DOC, although C18 was more selec-
tive for terrigenous compounds (Dittmar et al., 2008). The extract
from C18 SPE in disc form and original DOC from riverine samples
had a similar distribution of functional groups, indicated from
nuclear magnetic resonance (NMR) analysis (Kim et al., 2003).
Therefore, many studies investigating dissolved lignin degradation
products from freshwater (Louchouarn et al., 2000), estuarine
water (Dittmar et al., 2007; Bianchi et al., 2009), oceans (Hernes
and Benner, 2006) and stalagmites (Blyth and Watson, 2009) have
favoured C18 SPE. Comparison of solvents such as MeOH or MeCN
to activate and elute sorbed fresh, estuarine and marine DOC from
C18 SPE cartridges found little difference in cinnamyl:vanillyl (C:V),
syringyl:vanillyl (S:V) and acid:aldehyde ratios, although greater
recovery of freshwater K8 lignin phenols was achieved using
MeOH (76.2–91.1%, mean 86.0%) than MeCN (48.3–77.4%, mean
67.4%) when compared with a sample prepared using rotary evap-
oration (Spencer et al., 2010).
Thermally assisted hydrolysis and methylation (THM) in the
presence of tetramethylammonium hydroxide (TMAH), sometimes
known as TMAH thermochemolysis, has been used off-line to anal-
yse DOC, soils and vegetation (Martín et al., 1995; del Rio et al.,
1998; Huang et al., 1998; Frazier et al., 2003). It has also been
employed on-line with gas chromatography – mass spectrometry
(GC–MS) to characterise the molecular components of plant litter,
soils, aquatic humic substances (Saiz-Jimenez et al., 1993;
Challinor, 1995; Clifford et al., 1995; Mason et al., 2009, 2012)
and terrestrial OM preserved in stalagmites (Blyth and Watson,
2009). One of its most interesting applications is in the character-
isation of phenolic compounds with side chains extending up to
three carbons formed from the TMAH-induced cleavage of ether
and ester bonds in plant-derived polyphenols present in soils
(e.g. Mason et al., 2012) and peat (e.g. Schellekens et al., 2015).
The aims of this study were to: (i) assess the yield from C18 SPE
during the extraction of water-transportable lignin phenols from a
range of natural freshwaters, and compare cold on-column GC and
on-line THM using TMAH to detect extracted waterborne phenols,
(ii) compare water TOC, total phenol concentration and phenolic
diversity from different land uses – grazed grassland, woodland
and moorland – chosen because they represent the three dominant
land use types in southwest England.
2. Material and methods
2.1. Sampling sites and collection
River, soil drainage and pond water samples were collected in
triplicate from six sites (Table 1) in the vicinity of Rothamsted
Research North Wyke, Devon, southwest England, UK [50°450
N,
4°530
W] across different land uses (grazed grassland, woodland
and moorland). The first replicate from each site was collected
on May 11, 2010. The second and third replicates from the sites
Grassland 1, Grassland 2, Woodland 1, Grassland 3 and River were
collected on July 21, 2010. The second and third replicates from
Woodland 2 were collected on January 24, 2011 since this site
was dry until then. Water samples were collected in a bucket
(15 l) to ca. half-full, before transferring a subsample (5 l) to two
amber glass bottles (2.5 l) on-site. Sample pH was measured and
all samples were adjusted to pH 2 by adding sufficient drops of
concentrated HCl (Trace analysis grade, 37%; Fisher Scientific)
and stored in a fridge until extraction.
2.2. Soil and livestock dung sampling
The soils were sampled from each of the grassland, woodland,
and moorland land use types (Table 1) which had adjacent water
outlets within 100 m for sampling. Fifteen soil cores (25 mm di.,
< 30 cm depth) were taken in 3 replicates of 5 in a ‘W’ spatial sam-
pling pattern using a soil auger for each land use. The O and A hori-
zons were separated for analysis, and the impermeable clay B
horizon was discarded. The 5 samples constituting each of the 3
replicates were homogenised.
Representative samples of fresh cattle and sheep dung solids
(n = 3) were collected from each of the grassland plots (Table 1).
2.3. Sample extraction
Total OC (TOC) content was determined for water samples
(CA14 Formacs, Skalar (UK) Ltd.). The carrier gas was purified air,
supplied by a TOC gas generator (scrubbed of CO2 and moisture),
Table 1
Geographical positions of sampling sites with Ordnance Survey national grid reference (G.R.) and land use descriptions. River is a mixed land use sample (moorland, grazed
grassland and woodland).
Sample Position and description G.R.
Grassland 1 Taw Barton Farm. Grazed grassland artificial drainage water SX654971
Grassland 2 Sticklepath. Mix of spring water & grazed grassland drainage SX641939
Grassland 3 Josephs Carr Pond in a wet mire SX654988
Woodland 1 Tributary of River Taw. Quercus robur dominated woodland SX665979
Woodland 2 Orchard Dean Copse. Seasonally flowing ditch in woodland SX653982
River River Taw, Moorland source, through grazed grassland and woodland SX653984
46 J.S. Williams et al. / Organic Geochemistry 102 (2016) 45–51
3. and the inorganic catalyst was 2% orthophosphoric acid. Water
samples were then extracted using FD or SPE (described below)
and analysed on the basis of a split-split-plot experimental design.
SPE of water samples was carried out using a published method
(Louchouarn et al., 2000) except that samples were not initially fil-
tered (0.2 lm). Reversed phase C18 end capped SPE cartridges
(60 ml, 10 g, Mega-Bond Elut; Agilent Technologies) were mounted
on a vacuum manifold (VAC ELUT-20, 13 Â 75 mm, Varian) con-
nected to a vacuum pump (Gast Diaphragm pump, model: DOA-
P504-BN; Gast Manufacturing, Inc., USA) via a liquid trap (Carboy
Bottle 20 l, part 2226-0050 with filling venting closure, part
2161-0830; Varian Ltd.), enabling up to 10 SPE cartridges to be
used simultaneously. Each cartridge was preconditioned with
100 ml MeOH (HPLC grade; Fisher Scientific) followed by 50 ml
pure water (MilliQ Gradient A10) acidified to pH 2 (Trace analysis
grade HCl acid, 37%; Fisher Scientific). Water (2.5 l) was drawn
through the SPE cartridges at an average rate of ca. 20 ml/min
via a Teflon transfer pipe (1/8 in. Â 0.1 in.; Part AL20096, Varian
Ltd.) and adapters (part 12131004, Varian Ltd.) to seal the SPE car-
tridge. After samples were extracted, cartridges were rinsed with
50 ml acidified pure water (pH 2) to remove any residual salts.
Louchouarn et al. (2000) rinsed with 1 l acidified water as they
analysed saline in addition to freshwater samples. Then, collection
bottles (60 ml; Part BTF-543-030X, Fisher Scientific) were placed
inside the vacuum manifold under each SPE cartridge prior to elut-
ing the retained WBM in one fraction with 50 ml MeOH. The MeOH
was evaporated from the collection bottles at 40 °C under a stream
of N2 and transferred quantitatively to a 5 ml glass vial before final
evaporation to dryness and being capped and stored under N2 in a
freezer until analysis. Procedural blanks (ultrapure Milli-Q water)
were analysed separately in order to assess potential contamina-
tion during sample handling.
2.4. Sample derivatisation and analysis
The dry WBM residues (ca. 3 mg) extracted using FD and SPE
were analysed for total C and total N using a Carlo Erba NA2000
analyser (CE Instruments, Wigan, UK) and a SerCon 20–22 isotope
ratio mass spectrometer (SerCon Ltd., Crewe, UK) at Rothamsted
Research North Wyke. Wheat flour (1.91% N, 41.81% C, 4.80 d15
N
and À26.41 d13
C) calibrated against IAEA-N-1 by Iso-Analytical,
Crewe, UK was used as a reference standard.
An aliquot of SPE (ca. 2 mg) extract was derivatised with N,O-
bis(trimethylsilyl)trifluoroacetamide (BSTFA) in a GC vial (part:
STV12-02L, Kinesis) with limited volume insert (part: INWC-01,
Kinesis), by dissolving in 50 ll pyridine, and whirlimixed for 15 s
with BSTFA (5 drops). Trimethylchlorosilane (TMCS, 1%) was added
before capping the vials and heating the samples at 60 °C for 1 h.
The samples were then blown down to dryness under N2. 5a-
Androstane (3 ll; 0.1 mg/ml) was added to each sample as an
internal standard. Samples were redissolved in dichloromethane
(DCM) and analysed using cold on-column GC with flame ionisa-
tion detection (GC-FID) for quantification and GC–MS for identifi-
cation of the trimethyl (TMS) derivatives.
Cold on-column GC-FID (HRGC 5160 Mega Series; Carlo Erba
Strumentazione) was used with a 60 m HP-5, 0.25 mm i.d.,
0.25 lm film thickness column (Agilent J&W). The GC oven pro-
gramme was 40 °C (2 min) to 300 °C (held 1 min) at 2 °C/min, then
to 320 °C (held 40 min) at 20 °C/min (run time 174 min). The car-
rier gas was H2 at 2 ml/min. Injection volume was 1 ll.
GC–MS analysis of the BSTFA-derivatised total solvent extract
was performed with an Agilent 7890A GC split/splitless injector
(280 °C) linked to an Agilent 5975C mass selective detector (elec-
tron voltage 70 eV, source 230 °C, quad 150 °C electron multiplier
(EM) 1800 V, interface 310 °C). Samples were manually injected
(1 ll) in splitless mode for 1 min before switching to an open split
(30 ml/min) using a 60 m HP5 ((5% phenyl)-methylpolysiloxane)
column (0.25 mm i.d., 0.25 lm film thickness; Agilent J&W Scien-
tific, USA) using the same GC oven temperature programme as
for GC-FID. H2 was the carrier gas at 1 ml/min. Product detection
was carried out in full scan mode (m/z 50–700), EM voltage was
2176 V. Acquisition was controlled with a HP Compaq computer
using Chemstation software.
An aliquot of SPE extracted WBM was analysed using THM with
TMAH. Extracted sample (ca. 1 mg) was weighed into a quartz
pyrolysis tube plugged with solvent-extracted glass wool. The glass
wool had been extracted with DCM:MeOH (93:7, v/v) in a Soxhlet
apparatus for 24 h. 5a-Androstane in DCM (3 ll; 0.1 mg/ml) was
added as internal standard to the pyrolysis tube. Immediately prior
to analysis, TMAH (5 ll; 25%; w/w in aqueous solution) was added.
The tube was inserted into the Pt pyrolysis coil and flash pyrolysed
at 610 °C for 10 s (20 °C/ms ramp). The temperature and ramp rate
were chosen as they were successful in previous studies investigat-
ing lignin phenols (Clifford et al., 1995; Huang et al., 1998; Mason
et al., 2009, 2012) and Sphagnum–derived phenols (Abbott et al.,
2013). The pyroprobe interface was maintained at 340 °C with
the products passing into an HP6890 GC instrument with an open
split (30 ml/min) and a 60 m HP5-MS column (0.25 mm i.d.,
0.25 lm film thickness; J&W Scientific, USA). He was the carrier
gas at 1 ml/min. The GC oven was programmed from 50 °C to
220 °C (held 1 min) at 1.5 °C/min, and then to 320 °C (held
16 min) at 15 °C/min. Detection was carried out using an HP5973
series mass selective detector (MSD) in full scan mode (m/z 50–
700). Identification was based on the NIST98 mass spectral library
as well as comparison with relative retention times and mass spec-
tra reported in other studies (Clifford et al., 1995; del Rio et al.,
1998; Chefetz et al., 2000; Nierop, 2001; Vane et al., 2001; Vane,
2003; Robertson et al., 2008; Mason et al., 2009, 2012).
2.5. Data presentation and statistical data analysis
Total lignin phenol concentration was normalised to 100 mg OC
for each site. The statistical data analysis was carried out using
analysis of variance (ANOVA) with GenStat 64-bit Release 14.1
and correlation using Microsoft Excel. Statistical significance was
tested at the 95% level, and Tukey’s 95% confidence intervals test
was used to identify statistical differences.
3. Result and discussion
3.1. WBM extraction yield
SPE recovered 11.92 ± 2.69, 0.30 ± 0.30, 20.97 ± 6.67,
8.97 ± 3.17, 6.93 ± 0.97 and 3.24 ± 0.95 mg/l of WBM from Grass-
land 1, Grassland 2, Grassland 3, Woodland 1, Woodland 2 and
River sites, respectively (Fig. 1b). The total weights of WBM recov-
ered with SPE are reported in Table 2.
Expressed as a concentration, the amount of WBM recovered
from the six water samples by SPE (Fig. 1b) correlated with water
TOC (Fig. 1a, r2
0.9542, P < 0.001). This confirms the organic nature
of the isolated WBM.
3.2. Phenol extract yield from THM and GC-FID
Phenols were components of the TMAH thermochemolysis
products from the SPE-extracted WBM at all 6 sites (Fig. 2) with
total phenol concentration ranging between 0.09 ± 0.05 (Grassland
2) and 0.82 ± 0.37 mg/100 mg OC (Grassland 1). Previously, C18 SPE
has demonstrated excellent recovery of lignin phenols (101 ± 4%)
and repeatability from freshwater samples compared with direct
dry-down (Louchouarn et al., 2000). The total concentration values
J.S. Williams et al. / Organic Geochemistry 102 (2016) 45–51 47
4. of SPE isolated phenols detected using THM for Grassland 2, Grass-
land 3, Woodland 1, Woodland 2 and River sites here were compa-
rable with total lignin phenol (K8) concentration determined from
freshwaters [Penobscot River, Maine (Spencer et al., 2010) and the
Big Pine Creek watershed (Dalzell et al., 2005)] using CuO oxida-
tion. Following SPE extraction, GC-FID only allowed phenols to
be detected at 4 of the 6 sites and in lower abundance than those
released during THM, with concentration ranging between
0 mg/100 mg OC in Grassland 2 and River to 0.05 mg/100 mg OC
in Grassland 1 (Fig. 2).
THM in the presence of TMAH released an increase of more than
one order of magnitude in the amount of phenols relative to the
amount detected with GC-FID for all the samples.
3.3. Phenol diversity in SPE extracts detected with THM or GC-FID
Following SPE and detection with GC-FID, some benzoic acids
were found as their respective TMS ethers and esters (abbreviated
to P6, G6, PA and S6) in 4 of the water samples (Grassland 1, Grass-
land 3, Woodland 1 and Woodland 2; Table 3). Grassland 1 con-
tained the highest OC-normalised amounts with P6, PA and G6
having 38.8, 3.4, and 3.6 lg/100 mg OC, respectively. No phenols
were detected in Grassland 2 or River sites. For Grassland 2, this
may be due to the very low level of total phenols (Fig. 2), whereas
for the River sample, it may be due to a large proportion of phenols
existing in oligomeric or particulate form not identifiable via GC-
FID. PA is the only acid in both Woodland 1 and Woodland 2 water
samples, which have a significant input from Quercus robur (oak).
In its underivatised form PA is 3,4-dihydroxybenzoic acid (proto-
catechuic acid) and has also been detected in oak dominated soils
in the Netherlands (Nierop and Filley, 2007).
TMAH thermochemolysis yielded significantly more phenols at
all 6 sites than from the GC-FID analysis of the WBM isolated from
each of the water samples with SPE (Fig. 2). These included vascu-
lar plant-derived phenols released by guaiacyl (G), syringyl (S) and
p-hydroxyphenyl (H) lignin units (Ralph et al., 2004) as well as
phenols (P) from other sources.
Thermochemolysis releases phenols produced from the TMAH-
induced cleavage of ether and ester bonds in the lignin macro-
molecule (Hatcher et al., 1995; Wysocki et al., 2008). A structurally
diverse range of phenolics, in higher concentration as well as in a
less oxidised form, were detected with THM than with GC-FID. This
suggests that a significant proportion of dissolved lignin phenols is
leached from the soil in an oligomeric form, rather than as
monomers.
3.4. Water TOC and phenols from different land uses
The TOC and lignin phenol parameters for the grazed grassland
and woodland water samples reflected ecosystem level inputs,
incorporating any interaction between the contributing inputs
within each ecosystem. The River sample was also subject to catch-
ment scale processes, including interactions between grazed grass-
land, woodland and moorland ecosystems. The Grassland 3 aquatic
sample (see Fig. 1a) had the highest TOC (13.86 ± 0.41 mg/l),
whereas water from the Grassland 2 site had the lowest TOC
(1.50 ± 0.75 mg/l, Fig. 1a), which were significantly different
(P < 0.001). The Grassland 2 aquatic OC concentration
(1.50 ± 0.75 mg/l) was also significantly different from the Grass-
land 1 sample (9.41 ± 2.64 mg/l), whereas water from the Wood-
land 1, Woodland 2 and mixed land-use River sites had
G
rassland
1
G
rassland
2
G
rassland
3
W
oodland
1
W
oodland
2
R
iver
G
rassland
1
G
rassland
2
G
rassland
3
W
oodland
1
W
oodland
2
R
iver
16
a b14
12
10
8
6
[TOC](mg/l)
WBMyield(mg/l)
4
2
0
30
25
20
15
10
5
0
Fig. 1. Mean (± standard error of mean, n = 3) of (a) TOC content of the water samples from different land use sites (Table 1); (b) total extract yield from SPE waterborne
matter (WBM).
Table 2
Mean (± standard error of mean in parentheses, n = 3) water sample pH, waterborne
matter (WBM) yield and TOC in solid phase extracted (SPE) WBM solid residues for 6
water samples from sites described in Table 1 (n.d., not detected).
Site pH WBM yield (mg) TOC of WBM residue (%)
Grassland 1 7.33 (0.20) 30.6 (7.9) 47.2 (2.2)
Grassland 2 6.39 (0.06) 2.5 (1.0) 59.1 (4.8)
Grassland 3 6.50 (0.21) 38.3 (14.0) 46.5 (3.4)
Woodland 1 7.14 (0.09) 23.9 (8.5) 44.2 (3.7)
Woodland 2 6.54 (0.01) 17.8 (0.9) 41.9 (2.9)
River 7.35 (0.18) 9.9 (2.7) 50.6 (2.0)
G
rassland
1
G
rassland
2G
rassland
3W
oodland
1
W
oodland
2
R
iver
Totalphenolconcentration(mg/100mgOC)
1.2
1.4
1.0
0.8
0.6
0.4
0.2
0.0
GC-FID
THM
Fig. 2. Mean (± standard error of mean, n = 3) total phenolic concentration from SPE
water samples detected using cold on-column GC-FID and THM. Sites are described
in Table 1.
48 J.S. Williams et al. / Organic Geochemistry 102 (2016) 45–51
5. statistically similar TOC concentrations (5.45 ± 1.60, 3.42 ± 0.46
and 2.32 ± 0.72 mg/l, respectively in Fig. 1a). Increased TOC con-
tent was measured in the Grassland 1 and 3 water as compared
with both woodland samples. Grassland 2 was probably diluted
by a contribution of underground spring water with low OM con-
tent (Fig. 1a). The TOC content of SPE extracted WBM was also
greater in grazed grassland than in woodland water samples
(Table 2). In another study, increased TOC values were also
detected in the leachates from grass litter-amended soil lysimeters
compared with ash and oak leaf litter-amended lysimeters, also
revealing that grass litter lost more OC as DOC than oak and ash lit-
ter (Williams et al., 2016).
Mean water pH (± standard error, n = 3) decreased as follows:
River (7.35 ± 0.18) > Grassland 1 (7.33 ± 0.20) > Woodland 1
(7.14 ± 0.09) > Woodland 2 (6.54 ± 0.01) > Grassland 3 (6.50 ±
0.21) > Grassland 2 (6.39 ± 0.06, Table 2).
Since SPE followed by THM was the better approach for detect-
ing and identifying lignin phenol biomarkers, this combination was
used to characterise the phenolic thermochemolysis product dis-
tributions with the aim of investigating a relationship with land
use. Fig. 2 shows that total dissolved phenols represented a rela-
tively minor component (0.09 ± 0.05% to 0.82 ± 0.37%) of DOC from
all ecosystems, comparable with total phenol concentrations in
leachates from lysimeter grass and woody leaf litter degradation
studies also detected with THM (Williams et al., 2016) as well as
in leaf litter itself (Klotzbücher et al., 2011; Williams et al.,
2016). This indicates little or no net additional soil contribution
to total phenolic concentration lost in the dissolved phase at the
lysimeter or ecosystem scale. Negligible amounts of phenols were
detected in the River sample with SPE followed by GC-FID (Table 3),
although SPE followed by THM of the same sample detected
similar total phenol concentration to the Grassland 3 sample. This
indicates that the phenols in the River sample were in oligomeric
form, so not identifiable with GC-FID.
G2 (3,4-dimethoxytoluene), G3 (3,4-dimethoxystyrene), P3 (4-
methoxystyrene) and P4 (4-methoxybenzaldehyde) were only pre-
sent in grassland-sourced water. These phenols have been detected
in grassland litter and soils (Huang et al., 1998; Mason et al., 2012).
G3 and P3 are also associated with non-woody lignin (Clifford
et al., 1995; Chefetz et al., 2000). S2 (3,4,5-trimethoxytoluene)
and S18 [trans-3-(3,4,5-trimethoxyphenyl)-propenoic acid methyl
ester) were present only in the Woodland 1 water sample.
Total lignin phenol concentration values in soil O and A hori-
zons, as well as animal dung and DOM from grazed grassland,
woodland and moorland are presented in Fig. 3. This comparison
shows that OC-normalised total lignin concentration for DOM in
the freshwater samples was similar to total lignin concentration
in soil O and A horizons, for their respective land uses (Fig. 3). This
suggests that all the different land uses export a similar amount of
lignin per unit weight of OC into the drainage water.
4. Conclusions
The amounts of vascular plant-derived phenols from THM were
more than an order of magnitude higher than those measured
using GC-FID in SPE extracted WBM, so SPE followed by THM
was recognised as the approach to recover and identify water-
transportable phenols. However, SPE is not able to recover phenols
in particulate form, so there may be an underestimation of the flux
of total waterborne lignin phenols lost from soils and ecosystems
using this method. All the different land uses investigated export
similar amounts of lignin per unit weight of OC into the drainage
waters.
Acknowledgments
We thank D. Dhanoa for assistance with statistical analysis, and
P. Donohoe and I. Harrison for analytical instrument support at
Table 3
Mean (± standard error of mean, n = 3) water-transportable benzoic acids concentrations, as TMS derivatives, from six sites (see Table 1), extracted using SPE and detection using
GC-FID (PA, protocatechuic acid; n.d., not detected).
TMS derivative Abbr Concentration (mg/100 mg OC)
Grassland 1 Grassland 2 Grassland 3 Woodland 1 Woodland 2 River
4-[(TMS)oxy]-benzoic acid TMS ester P6 38.75 (21.51) n.d. 0.28 (0.28) n.d. 0.08 (0.08) n.d.
3-Methoxy-4-[(TMS)oxy]-benzoic acid TMS ester G6 3.40 (2.82) n.d. 0.57 (0.57) 0.3 (0.3) n.d. n.d.
3,4-Bis[(TMS)oxy]-benzoic acid TMS ester PA 3.61 (0.70) n.d. 0.36 (0.36) 0.27 (0.27) 0.73 (0.73) n.d.
3,4,5-Tris(TMSoxy)-benzoic acid TMS ester S6 n.d. n.d. n.d. 1.63 (1.63) n.d. n.d.
Fig. 3. Mean (± standard error of mean, n = 3) total lignin phenol concentrations in soils, dung and DOM extracts (G, grazed grassland; F, woodland; M, moorland; subscripts o
and a denote the soil organic and A horizons respectively; SD, sheep dung; C, cattle dung).
J.S. Williams et al. / Organic Geochemistry 102 (2016) 45–51 49
6. Newcastle University. We also acknowledge financial support from
the Natural Environment Research Council (NERC, Reference: NE/
G011982/1) of the UK. We thank two anonymous reviewers for
helpful and constructive comments. The work represents part of
the BBSRC funded programmes at Rothamsted Research on Sus-
tainable Soil Function, and Bioenergy and Climate Change.
Associate Editor—P. Schaeffer
References
Abbott, G.D., Swain, E.Y., Muhammad, A.B., Allton, K., Belyea, L.R., Laing, C.G., Cowie,
G.L., 2013. Effect of water-table fluctuations on the degradation of Sphagnum
phenols in surficial peats. Geochimica et Cosmochimica Acta 106, 177–191.
Aiken, G.R., Thurman, E.M., Malcolm, R.L., Walton, H.F., 1979. Comparison of XAD
macroporous resins for the concentration of fulvic-acid from aqueous-solution.
Analytical Chemistry 51, 1799–1803.
Amador, J.A., Milne, P.J., Moore, C.A., Zika, R.G., 1990. Extraction of chromophoric
humic substances from seawater. Marine Chemistry 29, 1–17.
Benner, R., Opsahl, S., 2001. Molecular indicators of the sources and transformations
of dissolved organic matter in the Mississippi river plume. Organic
Geochemistry 32, 597–611.
Berner, E.K., Berner, R.A., 2012. Global Environment: Water, Air, and Geochemical
Cycles. Princeton University Press.
Bianchi, T.S., DiMarco, S.F., Smith, R.W., Schreiner, K.M., 2009. A gradient of
dissolved organic carbon and lignin from Terrebonne-Timbalier Bay estuary to
the Louisiana shelf (USA). Marine Chemistry 117, 32–41.
Blyth, A.J., Watson, J.S., 2009. Thermochemolysis of organic matter preserved in
stalagmites: a preliminary study. Organic Geochemistry 40, 1029–1031.
Bolan, N.S., Adriano, D.C., Kunhikrishnan, A., James, T., McDowell, R., Senesi, N.,
2011. Dissolved organic matter: biogeochemistry, dynamics, and
environmental significance in soils. Advances in Agronomy 110, 1–75.
Bowen, S.R., Gregorich, E.G., Hopkins, D.W., 2009. Biochemical properties and
biodegradation of dissolved organic matter from soils. Biology and Fertility of
Soils 45, 733–742.
Challinor, J., 1995. Characterisation of wood by pyrolysis derivatisation—gas
chromatography/mass spectrometry. Journal of Analytical and Applied
Pyrolysis 35, 93–107.
Chefetz, B., Chen, Y., Clapp, C.E., Hatcher, P.G., 2000. Characterization of organic
matter in soils by thermochemolysis using tetramethylammonium hydroxide
(TMAH). Soil Science Society of America Journal 64, 583–589.
Clifford, D.J., Carson, D.M., McKinney, D.E., Bortiatynski, J.M., Hatcher, P.G., 1995. A
new rapid technique for the characterisation of lignin in vascular plants:
thermochemolysis with tetramethylammonium hydroxide (TMAH). Organic
Geochemistry 23, 169–175.
Dalzell, B.J., Filley, T.R., Harbor, J.M., 2005. Flood pulse influences on terrestrial organic
matter export from an agricultural watershed. Journal of Geophysical Research:
Biogeosciences 110, G02011. http://dx.doi.org/10.1029/2005JG000043.
del Rio, J.C., McKinney, D.E., Knicker, H., Nanny, M.A., Minard, R.D., Hatcher, P.G.,
1998. Structural characterization of bio- and geo-macromolecules by off-line
thermochemolysis with tetramethylammonium hydroxide. Journal of
Chromatography A 823, 433–448.
Dittmar, T., Koch, B., Hertkorn, N., Kattner, G., 2008. A simple and efficient method
for the solid-phase extraction of dissolved organic matter (SPE-DOM) from
seawater. Limnology and Oceanography Methods 6, 230–235.
Dittmar, T., Whitehead, K., Minor, E.C., Koch, B.P., 2007. Tracing terrigenous
dissolved organic matter and its photochemical decay in the ocean by using
liquid chromatography/mass spectrometry. Marine Chemistry 107, 378–387.
Durack, P.J., Wijffels, S.E., Matear, R.J., 2012. Ocean salinities reveal strong global
water cycle intensification during 1950 to 2000. Science 336, 455–458.
Eckard, R.S., Hernes, P.J., Bergamaschi, B.A., Stepanauskas, R., Kendall, C., 2007.
Landscape scale controls on the vascular plant component of dissolved organic
carbon across a freshwater delta. Geochimica et Cosmochimica Acta 71, 5968–
5984.
Ertel, J.R., Hedges, J.I., Devol, A.H., Richey, J.E., De Nazare Goes Ribeiro, M., Ribeiro, G.,
1986. Dissolved humic substances of the Amazon River system. Limnology and
Oceanography 31, 739–754.
Frazier, S.W., Kaplan, L.A., Hatcher, P.G., 2005. Molecular characterization of
biodegradable dissolved organic matter using bioreactors and [12
C/13
C]
tetramethylammonium hydroxide thermochemolysis GC-MS. Environmental
Science & Technology 39, 1479–1491.
Frazier, S.W., Nowack, K.O., Goins, K.M., Cannon, F.S., Kaplan, L.A., Hatcher, P.G.,
2003. Characterization of organic matter from natural waters using
tetramethylammonium hydroxide thermochemolysis GC-MS. Journal of
Analytical and Applied Pyrolysis 70, 99–128.
Gardner, W.S., Menzel, D.W., 1974. Phenolic aldehydes as indicators of terrestrially
derived organic-matter in sea. Geochimica et Cosmochimica Acta 38, 813–822.
Goni, M.A., Ruttenberg, K.C., Eglinton, T.I., 1997. Source and contribution of
terrigenous organic carbon to surface sediments in the Gulf of Mexico. Nature
389, 275–278.
Guggenberger, G., Zech, W., 1994. Composition and dynamics of dissolved
carbohydrates and lignin-degradation products in two coniferous forests, N.E.
Bavaria, Germany. Soil Biology & Biochemistry 26, 19–27.
Hatcher, P.G., Nanny, M.A., Minard, R.D., Dible, S.D., Carson, D.M., 1995. Comparison
of two thermochemolytic methods for the analysis of lignin in decomposing
gymnosperm wood: the CuO oxidation method and the method of
thermochemolysis with tetramethylammonium hydroxide (TMAH). Organic
Geochemistry 23, 881–888.
Hedges, J.I., Parker, P.L., 1976. Land-derived organic matter in surface sediments
from the Gulf of Mexico. Geochimica et Cosmochimica Acta 40,
1019–1029.
Hedges, J.I., Keil, R.G., Benner, R., 1997. What happens to terrestrial organic matter
in the ocean? Organic Geochemistry 27, 195–212.
Hedges, J.I., Mann, D.C., 1979a. Characterisation of plant-tissues by their lignin
oxidation-products. Geochimica et Cosmochimica Acta 43, 1803–1807.
Hedges, J.I., Mann, D.C., 1979b. The lignin geochemistry of marine sediments from
the southern Washington coast. Geochimica et Cosmochimica Acta 43, 1809–
1818.
Hernes, P.J., Robinson, A.C., Aufdenkampe, A.K., 2007. Fractionation of lignin during
leaching and sorption and implications for organic matter ‘‘freshness”.
Geophysical Research Letters 34, L17401.
Hernes, P.J., Benner, R., 2006. Terrigenous organic matter sources and reactivity in
the North Atlantic Ocean and a comparison to the Arctic and Pacific oceans.
Marine Chemistry 100, 66–79.
Huang, Y., Eglinton, G., Van der Hage, E.R.E., Boon, J.J., Bol, R., Ineson, P., 1998.
Dissolved organic matter and its parent organic matter in grass upland soil
horizons studied by analytical pyrolysis techniques. European Journal of Soil
Science 49, 1–15.
Kalbitz, K., Schwesig, D., Rethemeyer, J., Matzner, E., 2005. Stabilization of dissolved
organic matter by sorption to the mineral soil. Soil Biology & Biochemistry 37,
1319–1331.
Kalbitz, K., Solinger, S., Park, J.H., Michalzik, B., Matzner, E., 2000. Controls on the
dynamics of dissolved organic matter in soils: a review. Soil Science 165, 277–
304.
Kim, S., Simpson, A.J., Kujawinski, E.B., Freitas, M.A., Hatcher, P.G., 2003. High
resolution electrospray ionization mass spectrometry and 2D solution NMR for
the analysis of DOM extracted by C18 solid phase disk. Organic Geochemistry
34, 1325–1335.
Klotzbücher, T., Kaiser, K., Guggenberger, G., Gatzek, C., Kalbitz, K., 2011. A new
conceptual model for the fate of lignin in decomposing plant litter. Ecology 92,
1052–1062.
Lara, R.J., Thomas, D.N., 1994. XAD-fractionation of new dissolved organic-matter –
is the hydrophobic fraction seriously underestimated. Marine Chemistry 47,
93–96.
Louchouarn, P., Opsahl, S., Benner, R., 2000. Isolation and quantification of dissolved
lignin from natural waters using solid-phase extraction and GC/MS. Analytical
Chemistry 72, 2780–2787.
Martín, F., del Rio, C., González-Vila, F.J., Verdejo, T., 1995. Thermally assisted
hydrolysis and alkylation of lignins in the presence of tetra-alkylammonium
hydroxides. Journal of Analytical and Applied Pyrolysis 35, 1–13.
Mason, S.L., Filley, T.R., Abbott, G.D., 2009. The effect of afforestation on the soil
organic carbon (SOC) of a peaty gley soil using on-line thermally assisted
hydrolysis and methylation (THM) in the presence of 13
C-labelled
tetramethylammonium hydroxide (TMAH). Journal of Analytical and Applied
Pyrolysis 85, 417–425.
Mason, S.L., Filley, T.R., Abbott, G.D., 2012. A comparative study of the molecular
composition of a grassland soil with adjacent unforested and afforested
moorland ecosystems. Organic Geochemistry 42, 1519–1528.
Meybeck, M., 1982. Carbon, nitrogen, and phosphorus transport by world rivers.
American Journal of Science 282, 401–450.
Meyersschulte, K.J., Hedges, J.I., 1986. Molecular evidence for a terrestrial
component of organic-matter dissolved in ocean water. Nature 321, 61–63.
Moran, M.A., Wicks, R.J., Hodson, R.E., 1991. Export of dissolved organic-matter
from a mangrove swamp ecosystem – evidence from natural fluorescence,
dissolved lignin phenols, and bacterial secondary production. Marine Ecology
Progress Series 76, 175–184.
Nierop, K.G.J., 2001. Temporal and vertical organic matter differentiation along a
vegetation succession as revealed by pyrolysis and thermally assisted
hydrolysis and methylation. Journal of Analytical and Applied Pyrolysis 61,
111–132.
Nierop, K.G.J., Filley, T.R., 2007. Assessment of lignin and (poly-)phenol
transformations in oak (Quercus robur) dominated soils by 13
C-TMAH
thermochemolysis. Organic Geochemistry 38, 551–565.
Ralph, J., Lundquist, K., Brunow, G., Lu, F., Kim, H., Schatz, P.F., Marita, J.M., Hatfield,
R.D., Ralph, S.A., Christensen, J.H., Boerjan, W., 2004. Lignins: natural polymers
from oxidative coupling of 4-hydroxyphenylpropanoids. Phytochemistry
Reviews 3, 29–60.
Rimmer, D.L., 2006. Free radicals, antioxidants, and soil organic matter
recalcitrance. European Journal of Soil Science 57, 91–94.
Rimmer, D.L., Abbott, G.D., 2011. Phenolic compounds in NaOH extracts of UK soils
and their contribution to antioxidant capacity. European Journal of Soil Science
62, 285–294.
Robertson, S.A., Mason, S.L., Hack, E., Abbott, G.D., 2008. A comparison of lignin
oxidation, enzymatic activity and fungal growth during white-rot decay of
wheat straw. Organic Geochemistry 39, 945–951.
50 J.S. Williams et al. / Organic Geochemistry 102 (2016) 45–51
7. Saiz-Jimenez, C., Hermosin, B., Ortega-Calvo, J.J., 1993. Pyrolysis/methylation – a
method for structural elucidation of the chemical nature of aquatic humic
substances. Water Research 27, 1693–1696.
Schellekens, J., Bradley, J., Abbott, G.D., Fraga, I., Buurman, P., Pontevedra-Pombal,
X., Vidal-Torrado, P., 2015. The use of plant-specific pyrolysis products as
biomarkers in peat deposits. Quaternary Science Reviews 123, 254–264.
Simpson, N.J.K., 2000. Solid-Phase Extraction: Principles, Techniques, and
Applications. Marcel Dekker Inc., New York.
Spencer, R.G.M., Aiken, G.R., Dyda, R.Y., Butler, K.D., Bergamaschi, B.A., Hernes, P.J.,
2010. Comparison of XAD with other dissolved lignin isolation techniques and a
compilation of analytical improvements for the analysis of lignin in aquatic
settings. Organic Geochemistry 41, 445–453.
Tian, Y.Q., Yu, Q., Feig, A.D., Ye, C., Blunden, A., 2013. Effects of climate and land-
surface processes on terrestrial dissolved organic carbon export to major U.S.
coastal rivers. Ecological Engineering 54, 192–201.
Vane, C.H., 2003. The molecular composition of lignin in spruce decayed by white-
rot fungi (Phanerochaete chrysosporium and Trametes versicolor) using pyrolysis-
GC-MS and thermochemolysis with tetramethylammonium hydroxide.
International Biodeterioration & Biodegradation 51, 67–75.
Vane, C.H., Martin, S.C., Snape, C.E., Abbott, G.D., 2001. Degradation of lignin in
wheat straw during growth of the oyster mushroom (Pleurotus ostreatus) using
off-line thermochemolysis with tetramethylammonium hydroxide and solid-
state 13
C NMR. Journal of Agricultural and Food Chemistry 49, 2709–2716.
Wang, X., Goual, L., Colberg, P.J.S., 2012. Characterization and treatment of dissolved
organic matter from oilfield produced waters. Journal of Hazardous Materials
217, 164–170.
Williams, J.S., Dungait, J.A., Bol, R., Abbott, G.D., 2016. Contrasting temperature
responses of dissolved organic carbon and phenols leached from soils. Plant and
Soil, 1–15. http://dx.doi.org/10.1007/s11104-015-2678-z.
Wysocki, L.A., Filley, T.R., Bianchi, T.S., 2008. Comparison of two methods for the
analysis of lignin in marine sediments: CuO oxidation versus
tetramethylammonium hydroxide (TMAH) thermochemolysis. Organic
Geochemistry 39, 1454–1461.
J.S. Williams et al. / Organic Geochemistry 102 (2016) 45–51 51