Maximum limits of heavy metals in soil, according with Canadian and Dutch standards (ppm) [4]
\r\n\tMany tried to define it, and its definition is always related to those who are in power, that being explained by the fact that this power and the abuse of it precisely, gives the access to being corrupted and practicing the acts that fall under corruption.
\r\n\r\n\tWe can find various types of corruption such as bribery, lobbying, extortion, cronyism, nepotism, parochialism, patronage, influence peddling, graft, and embezzlement. Also giving or accepting bribes or inappropriate gifts, double-dealing, under-the-table transactions, manipulating elections, diverting funds, laundering money, and defrauding investors.
\r\n\tNo government is immune to corruption. According to the World Bank, “the causes of corruption are always contextual, rooted in a country's policies, bureaucratic traditions, political development, and social history”.
\r\n\tThis indeed has consequences for increasing inequality, impacts government expenditure and services, shadow economy, and crime.
\r\n\tThis book will be a collection of chapters on Corruption. It welcomes contributions related to the nature of corruption its types and how corruption is undertaken in a certain context and the ways to deal with corruption will be part of this book. We value including materials on Corruption in organizations and ways to solve it. The origins of corruption and the way to deal with corruption, how to provide solutions, and any new insights on corruption will be part of this book.
",isbn:"978-1-80356-696-2",printIsbn:"978-1-80356-695-5",pdfIsbn:"978-1-80356-697-9",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!0,isSalesforceBook:!1,isNomenclature:!1,hash:"9cda6d2feaa52a6d523da74f2e2d7ffb",bookSignature:"Dr. Josiane Fahed-Sreih",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/11772.jpg",keywords:"Corruption, Origins, Types, Corporate Governance, Organizational Performance, Solutions, Corruption Index, Private Sector, Lebanon, Accountability, Anti-corruption, Public Policy",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"March 23rd 2022",dateEndSecondStepPublish:"April 20th 2022",dateEndThirdStepPublish:"June 19th 2022",dateEndFourthStepPublish:"September 7th 2022",dateEndFifthStepPublish:"November 6th 2022",dateConfirmationOfParticipation:null,remainingDaysToSecondStep:"a month",secondStepPassed:!0,areRegistrationsClosed:!1,currentStepOfPublishingProcess:3,editedByType:null,kuFlag:!1,biosketch:"Dr. Fahed-Sreih is the director of the Institute of Family and Entrepreneurial Business and a chairperson in the Department of Management. She obtained a Ph.D. from Sorbonne University, France, and received the 2007 FFI International Award for outstanding achievement in furthering the understanding of family business issues between two or more countries. She is on the editorial board of the Journal of Family Business Management and a keynote speaker for corporate governance conferences.",coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"103784",title:"Dr.",name:"Josiane",middleName:null,surname:"Fahed-Sreih",slug:"josiane-fahed-sreih",fullName:"Josiane Fahed-Sreih",profilePictureURL:"https://mts.intechopen.com/storage/users/103784/images/system/103784.jfif",biography:"Dr. Josiane Fahed-Sreih is a full-time associate professor of Management in the School of Business, Lebanese American University. She is the founder and director of the Institute of Family and Entrepreneurial Business and a chairperson in the Department of Management at the same university. She was previously the assistant dean. She obtained a Ph.D. from Sorbonne University, Paris, France. Dr. Fahed-Sreih is the Middle East Coordinator for the Family Firm Institute (FFI), the USA, and a family wealth and family business consultant. She received the 2007 FFI International Award for outstanding achievement in furthering the understanding of family business issues that occur between two or more countries. She has participated in and organized international conferences, workshops, and seminars. She has presented at major conferences locally and internationally and consulted on management issues in many countries, including Saudi Arabia, Dubai, Jordan, Qatar, Kuwait, Syria, Bahrain, Oman, France, Cyprus, and Lebanon. She currently sits on five boards of directors as a shareholder, two as a chairman of the board, and one as an independent director in the private sector. She is also an advisor on boards of community service organizations. \n\nShe speaks regularly to trade and professional groups and presents her research at academic conferences worldwide. She is frequently invited as a keynote speaker to the recognized family business and corporate governance conferences. Her research interests are in management, family business, the functioning of boards of directors, and corporate governance. She has published three books, several book chapters, and academic articles in international journals. 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From chapter submission and review to approval and revision, copyediting and design, until final publication, I work closely with authors and editors to ensure a simple and easy publishing process. I maintain constant and effective communication with authors, editors and reviewers, which allows for a level of personal support that enables contributors to fully commit and concentrate on the chapters they are writing, editing, or reviewing. I assist authors in the preparation of their full chapter submissions and track important deadlines and ensure they are met. I help to coordinate internal processes such as linguistic review, and monitor the technical aspects of the process. As an ASM I am also involved in the acquisition of editors. 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Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"72",title:"Ionic Liquids",subtitle:"Theory, Properties, New Approaches",isOpenForSubmission:!1,hash:"d94ffa3cfa10505e3b1d676d46fcd3f5",slug:"ionic-liquids-theory-properties-new-approaches",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/72.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"314",title:"Regenerative Medicine and Tissue Engineering",subtitle:"Cells and Biomaterials",isOpenForSubmission:!1,hash:"bb67e80e480c86bb8315458012d65686",slug:"regenerative-medicine-and-tissue-engineering-cells-and-biomaterials",bookSignature:"Daniel Eberli",coverURL:"https://cdn.intechopen.com/books/images_new/314.jpg",editedByType:"Edited by",editors:[{id:"6495",title:"Dr.",name:"Daniel",surname:"Eberli",slug:"daniel-eberli",fullName:"Daniel Eberli"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"57",title:"Physics and Applications of Graphene",subtitle:"Experiments",isOpenForSubmission:!1,hash:"0e6622a71cf4f02f45bfdd5691e1189a",slug:"physics-and-applications-of-graphene-experiments",bookSignature:"Sergey Mikhailov",coverURL:"https://cdn.intechopen.com/books/images_new/57.jpg",editedByType:"Edited by",editors:[{id:"16042",title:"Dr.",name:"Sergey",surname:"Mikhailov",slug:"sergey-mikhailov",fullName:"Sergey Mikhailov"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"1373",title:"Ionic Liquids",subtitle:"Applications and Perspectives",isOpenForSubmission:!1,hash:"5e9ae5ae9167cde4b344e499a792c41c",slug:"ionic-liquids-applications-and-perspectives",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/1373.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"46304",title:"Assessment of Historical Heavy Metal Pollution of Land in the Proximity of Industrial Area of Targoviste, Romania",doi:"10.5772/58304",slug:"assessment-of-historical-heavy-metal-pollution-of-land-in-the-proximity-of-industrial-area-of-targov",body:'Contamination of soil and water with organic and inorganic pollutants is a subject of interest to European policy, looking for new ways of preventing pollution and remediating polluted sites. Source and type of contamination influences the nature of pollution and methods of remediation. Thus, accidental discharge can be isolated more easily from a small area of soil, while the contamination of water is more difficult to control. Deposition of particulate matter can contaminate wide surfaces with low concentrations of contaminants. However, particulate matter is the main source of contamination of soils with heavy metals.
Many international researches have studied the concentrations of metals in soil, in correlation with texture, structure and pH of soil. In order to reduce the concentration of heavy metal to a level allowing development of all crop plants under a secure intake level of heavy metals, pollution mitigation measures should be applied on those soils. Depending on land use, the legislation of each country establishes the normal and maximal limits of heavy metals in soil.
The development of metallurgical activities in an irresponsible manner and without taking into account the environmental damage, lead to a historical accumulation of heavy metals in soil. The concentration of heavy metals in soil varies significantly depending on the type of soil and geographic region. This indicates that the parental material, climatic conditions and human activities have a predominant impact on the chemical forms (speciation) and on the mobility of metals in soil. In addition to the methods of prevention and mitigation of pollutants emissions, there are a number of methods of remediation, based on soil stripping and replacement or methods of bioremediation.
Across Europe, an extensive study was conducted concerning the concentration of heavy metals in soil [1], involving the collaboration of several organizations: EuroGeo Survey, Geological Survey of Finland (GTK) and the Forum of European Geological Survey Directors (FOREGS). The project was conducted between 1996 and 2003, but unfortunately did not cover the Romanian territory. At the end of the project were drawn distribution maps of all metals in soils and sediments found along rivers and a Geochemical Atlas of Europe was designed.
Another significant study is Alina Kabata-Pendias book "Trace Elements in Soils and Plants" published so far in four editions [2]. This book provides a concise but comprehensive overview of the biogeochemistry of trace elements found in the soil-plant system. Includes over 400 references to recent studies that have been conducted to determine the metal content of the soil-plant system and highlights the significance of anthropogenic factors leading to the change of state elements in soil and plants. Subjects are bioindicators behaviour in the environment, soil remediation, and hyperaccumulation and hyperextraction of heavy metals from soil.
Organizations such as the Food and Agriculture Organization (FAO) and World Health Organization (WHO) have established very comprehensive reports related to the concentration of metals in food and doses considered daily necessary, maximum intake for different age groups, maximum limits in food and soils (Table 1). In Romania, the reference values for trace metals in soils are governed by Order 756 / 3rd of November 1997 [3]. It regulates normal values, alert thresholds and action levels for different trace elements by use of soils.
\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t||||
\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t|
Cu | \n\t\t\t150 | \n\t\t\t100 | \n\t\t\t150 | \n\t\t\t36 | \n\t\t\t100 | \n\t\t\t500 | \n\t\t
Zn | \n\t\t\t600 | \n\t\t\t500 | \n\t\t\t600 | \n\t\t\t140 | \n\t\t\t500 | \n\t\t\t3000 | \n\t\t
Cd | \n\t\t\t3 | \n\t\t\t5 | \n\t\t\t3 | \n\t\t\t0, 8 | \n\t\t\t5 | \n\t\t\t20 | \n\t\t
Pb | \n\t\t\t375 | \n\t\t\t500 | \n\t\t\t375 | \n\t\t\t85 | \n\t\t\t150 | \n\t\t\t600 | \n\t\t
Maximum limits of heavy metals in soil, according with Canadian and Dutch standards (ppm) [4]
The present study completes FOREGS project and aims to establish the concentrations of heavy metals in an industrial area, near the city of Targoviste. Depending on the climatic characteristics, on topography and on pollution rose, we have established representative points of soil sampling for the area. Samples were collected from both the surface of soil to determine the horizontal distribution of heavy metals in the industrial area, as well as on profile (0-40 cm) to determine the vertical distribution of the metals and to assess the extent of historical pollution.
The problem of soil contamination with heavy metals, fuel and other toxic materials is a reality worldwide. Following the accidents which occurred with discharges of toxic materials on the ground, the affected area increased by infiltration of substances into groundwater. The groundwater is carrying the pollutants to residential areas, endangering the health of residents.
Transfer of metallic particulate to human body
Heavy metals are natural components, which occurred in high concentrations under natural conditions. In the twentieth century, metalliferous uploading of air, water, soil and therefore of plants and the human body, has become an important concern of international researchers. Heavy metals are considered a risk for living organisms because they tend to bioaccumulate. Bioaccumulation is an increase of concentration of a chemical in living organisms, as compared to the concentration of the element in the environment. Compounds are accumulated in living organisms by uptake from environment and storage at a higher rate than that of metabolism or excretion.
Emissions from metallurgical plants are transported by air masses and then deposited on the ground, leading to an increase of metal concentration in the upper layer of soil. Plants, perennial grasses especially have a high storage capacity of such metals in their shoots. The plants loaded with large amounts of heavy metals are consumed by animals that are grazing of this land (Figure 1).
Metal concentration in soil varies significantly depending on the soil type, but also by region [5, 6]. This indicates that the parent material and climatic conditions have a predominant impact on the chemical state of metals in soil. Kabata-Pendias and Krakowiak [7] set a factor of soil parameters (RDI - Relative explanation index) based on the calculation of correlation coefficients matrix for metals and some soil parameters: pH, clay content, cation exchange capacity, substance the organic content of the soil and iron. For approx. 1000 samples, the strongest positive linear correlation was obtained for metals and fine fraction of the soil. This relationship varies for the metals studied and is well illustrated by the content of heavy metals in soil which increases with increasing clay content. The highest value of the RDI when correlated with clay content (60-75%) was calculated on Zn, Fe, Ni and Cr, while the lower value (10-30%) was calculated for Cd, Pb, Cu, and Mn (Figure 2).
Relative explanation index (RDI), of statistically significant relationship at 99% confidence level, between heavy metals in soil and clay content < 0.02 mm (a) and cation exchange capacity in soil (b) [
Copper (Cu) is an important element for all life forms, but can be toxic in high concentrations. The average Cu content in the lithosphere is 70 ppm. In natural soils, the average concentration is 2-40 ppm. As described for Ni, Cu has no similarities with any other metal regarding his chemical behaviour in soil. Significant quantities of Cu in the soil are connected in the minerals, therefore, this metal is supplied only by a very slow decay processes. Cu may occur in the form of readily soluble salts (copper nitrate, copper sulphate), and as an oxide and hydroxide. It binds to organic matter, ferric oxide and Al. Intake of Cu in plants can be increased by low pH and organic fertilizers. Cu concentration can increase significantly under the effect of anthropogenic activities (non-ferrous metal processing, the use of substances for plant protection). In humans, the contamination has not yet been notified by the dietary intake of Cu in the body, but its high concentration may cause liver damage.
Zinc (Zn) is widespread in nature and the average content of Zn in the lithosphere is about 80 ppm. Unpolluted soil contains an average of 15-100 ppm of Zn. Zinc binds to organic matter and ferric and Mn oxides. It occurs in large amounts in the layers of the clay minerals. Under natural conditions, in A horizon of soil from wet areas, with slightly acid pH, more than half of the Zn is bound to organic material [4]. Because of the extensive use of Zn in industry, the Zn content in soil surrounding the industrial areas can reach even 5000 ppm [2]. The effect of Zn is particularly harmful because its accumulation leads to accumulation of other heavy metals, such as Pb, Cu and cadmium (Cd). Concomitantly, in the lime-rich soils, the plants show Zn deficiency symptoms. Also, Cd is strongly chemical bond to the Zn, as the proportion Zn/Cd in soil is constant. The availability to plants can be influenced by the concentration of cadmium in soil, pH conditions, temperature, amount of organic matter, and presence of other metals. Cadmium is irreversibly bound by ferric and manganese oxides in soil, and by clay minerals that influence the Cd mobility.
Lead (Pb) in soil is largely associated with colloidal organic matter, which results in a high proportion of Pb accumulated in the top 5-15 cm of contaminated soils. The Pb concentration decreases with depth in a soil profile [2]. In the geosphere, the average Pb concentration is about 16 ppm. The increasing of Pb concentration may be caused by the accumulation of fuel combustion residues from the transportation, by application of sewage sludge and by the use of some pesticides in gardens or orchards. Increasing soil pH may decrease the absorption of Pb in soil. Plants are able to accumulate significant amounts of Pb (300-400 ppm) in pollution conditions without noticeable symptoms [2]. High concentration of Pb particularly affects the neurovegetative functions, hampers blood and cause chronic emphysema in humans.
Tin (Sn) concentrations in soil are generally low, with values of 2-3 mg/kg in unpolluted areas and can reach 200 – 1000 mg/kg in areas of high tin deposits [8] or in areas influenced by anthropogenic activities including smelters of ferrous and non-ferrous metals and coal-fired power plant [9].
Cobalt (Co) is widely distributed in rocks and soils and always occurs in nature in association with nickel and usually with arsenic [10]. The common Co minerals are smaltite (CoAs2) and cobaltite (CoAsS) and the most important sources of cobalt are residues from the smelting of arsenical ores of nickel, cobalt and lead [10]. Cobalt in environment may represent a hazard to human health and is considered a metal with marked allergenic potential.
Chromium (Cr) is used in alloying metals, in the industry of paints, cement, paper, rubber and other materials. Exposure to low concentrations of Cr produce skin irritation and ulceration, and long-term exposure can cause kidney and liver diseases, and diseases of the circulatory system and nervous tissue. Chromium accumulates especially in aquatic fish and the consumption increases the risk of a high intake of this metal.
Nickel (Ni) is necessary in small quantities in the human body to produce red blood cells [4], but greater amounts (>1.0 mg/d) may become toxic. Short-term exposure to Ni does not cause health problems, but over a long period leads to weight loss, heart and liver diseases, and skin irritation. Nickel can accumulate in aquatic organisms, but its presence increases for higher levels on the food chain.
Manganese (Mn) is a metal naturally ubiquitous in the environment, found in many types of rocks and soil, essential for normal physiologic functioning in humans and animal. Exposure to low levels of Mn is considered to be nutritional for humans. Long-term exposure to high levels of Mn by inhalation in humans may result in central nervous system effects. The metallic Mn is used in steel production to improve hardness, stiffness and strength. Mn is also used in carbon steel, stainless steel and high-temperature steel, along with cast iron and superalloys [11]. The average Mn levels in soil range from 40 to 900 ppm [11].
Molybdenum (Mo) is a valuable alloying agent which contributes to the hardness and toughness of quenched and tempered steels. Mo also improves the strength of steel at high temperature. In the environment, Mo differs from the other micronutrients in soils because it is less soluble in acid and more soluble in alkaline soils. Mo availability to plants is sensitive to pH and drainage conditions. Some plants can have up to 500 ppm of the metal when they grow on alkaline soils [12].
The presence of heavy metals in natural and contaminated soils shows a great variability in both the horizontal and vertical dimensions [2]. Chemical pollution of soils in Romania is affecting approx. 0.9 million ha of soil, of which 0.2 million ha are affected by excessive pollution. Adverse effects are particularly strong to pollution by heavy metals (Cu, Pb, Zn, Cd) and sulphur dioxide, identified especially in Baia Mare, Zlatna and Copsa Mica. Although in last years a number of industrial units have been closed and others have reduced activity, the soil pollution is quite high in some areas: Targu Mures, Turnu Magurele, Tulcea and Slatina. Oil pollution and salt water from oil wells and transport affects approximately 50, 000 ha. Soil damaged by excavation comprises 15, 000 ha and constitutes the most serious form of damage to soil, encountered in the mining industry, for example in the mining basin of Oltenia. Suitability of land affected by this type of pollution decreased by 1-3 classes, and some of these areas has become unproductive. Soil cover with solid waste and residues caused sealing of approximately 18 000 ha of farmland and meadows [13]. Direct economic damage on agricultural production due to these restrictions is estimated by reducing it by about 20% per year.
The study of Lăcătuşu and Ghelase [14] aimed to assess the abundance of anthropogenic heavy metals in soils at various distances from Romfosfochim SA Valea Călugărească. The researchers compared the specific data of metal concentrations in polluted soils with those of similar soils, not subject to pollution effects. The results showed a decrease in the percentage of geogenic abundance with proximity to the source of pollution, although the concentrations of Cu, Pb, Zn and Cd are significantly higher at distances between 0-500 m compared to the distance of 6 km [14]. The depth of penetration into the soil of heavy metals from industrial emissions is shallow (up to 15 cm) in forest soils and up to 30-40 cm in arable soils [15].
Vrînceanu et al. [16] have published the results of research on polluted soils from Copsa Mica, showing metal concentrations for Cu, Zn, Pb and Cd in soil, with values between 69-136 mg/kg, 962-2191 mg/kg, 1182 -1978 mg/kg and 30-42 mg/kg respectively. In 2002 a study showed that in the soil from Baia Mare the Cu concentration exceeded 9.5 times the maximum limits and 4.8 times the alert and action limits. The concentration of Pb exceeded 132 times the alert threshold and 66 times the limit of intervention and the concentration of Zn exceeded 11 and 6 times these limits respectively [17]. Recent researches in Baia Mare showed some decreasing of heavy metal concentration, but the average values of these concentrations exceed 6 times the maximum level of lead. In the case of Cu, Zn and Cd the average values exceed the maximum level by 10, 3 and 7 times. Multiple pollution average index for the four heavy metals determines the classification of this area as excessive pollution class (values greater than 16) in the layer of 0-10 cm and as very strong pollution class in the layer of 10-20 cm. The maximum values of this index reached 78.2 in some excessively polluted areas. In 1994, a land of 21, 875 ha (3, 245 ha of forest and 18, 630 ha of agricultural land) have been severely affected by heavy metal pollution by exceeding the maximum limits for Pb, Cu, Zn and Cd [16].
Maximum levels of metal pollution were detected in Baia Mare for Cd, in Copşa Mica for Pb and Zn, and in Valea Călugărească for Cu [15]. Besides these considerations we can add the ecological accident occurred at Baia Mare in 2000 that led to the contamination of water and soil with cyanide from extraction plants. Specific conditions of those soils (moderate to severe acidity) are favouring the translocation of pollutants from soil to plants, animals and humans, leading to an increase of metal toxicity and a reduction of soil and water quality. Research conducted in 2000 in several areas in the south of Romania have shown the persistence of severe soil pollution with heavy metals in the vicinity of industrial plants (S.C. Neferal and S.C. Acumulatorul-Bucureşti-Pantelimon, S.C. Turnu S.A. – Turnu Măgurele) and pollution with fluoride near ALRO-Slatina.
All these environmental assessments showed the necessity of soil quality improving policy, by changing the land use and by replacing the food crops with industrial crops. Also these areas need measures to reduce the pollution and its toxic effects. Exploit of Romanian peat deposits for the purpose of complete the organic matter of soil, could be a source for improving soil quality and reducing pollution [18].
A global statistical evaluation of the substances exchange between soil and plants, led to the conclusion that the percentage itself is influenced by the following parameters:
Soil texture;
Carbon content of organic substances;
Cation exchange capacity of the soil;
Calcium carbonate equivalent;
Oxides and hydroxides, mainly Fe, Mn and Al;
pH values - dominant factor.
Soil organic fraction plays an extremely important role because they can delay both the accumulation and transfer of metals and their movement into the soil. Metal toxicity in soil can be increased or reduced by soil organic fraction. Soil pH directly influences the availability of metals as soil acidity determines solubility of element and its ability to move in the soil solution. Regarding the content of phosphorus in soil, the presence of high doses of P2O5 can increase or decrease metal uptake. In addition, the accumulation of metals is directly influenced by the plant physiology. For example, Cd uptake in grain has been described to be either antagonistic or synergistic with high concentrations of Pb in the soil [19].
In discussions about soil protection and remediation, pollutant limits for various elements have been established only under certain conditions and soil parameters. It was not taken into account the specific conditions such as the fact that on low-carbon light soils there is strong influence of rainfall leading to a strong acid mobilization and uptake into plants of toxic heavy metals. This does not happen on heavier soils rich in limestone.
The solubility of Zn in soil was studied by Herms and Brummer [20], which demonstrated the extent to which this element is dissolved by increasing acidity of the soil and became available for plants uptake. A pH value of 5 of low-Zn soil could lead to lasting effect of uptake large amounts of Zn, with all the negative consequences that result. The balance of Zn in the soil solution is carried out according to the pH of soil: at 1200 mg/kg of Zn and a pH of 7, at 100 mg/kg of Zn and pH of 6, and at only 40 mg/kg Zn and a pH of 5. This indicates that also the low-Zn soil can store dangerous amounts of available Zn.
Metallurgy activities produce gas, wastewater and waste containing pollutants that can be sources of risk under normal handling, and especially for irresponsible handling of equipment. The main resulted pollutants are: CO2, CO, NO, SO, VOCs (e.g. BaP, PAHs, dioxins, Freon), particulate heavy metals (Pb, Cu, Zn, As, Cr), cyanides, phenols, heavy metals and sometimes toxic organic compounds in waste material.
Annual average concentrations exceed the maximum permitted levels in many localities (Baia Mare, Copsa Mica, Medias, Targoviste, Arad, Deva, etc.), for both particulate matter and for sediment, coming mainly from industry of steel.
The main polluter from industrial zone of Targoviste city was SC Mechel Targoviste SA, located in the south of the city. By the metallurgical activity, emissions were resulting, with significant concentrations of pollutants, including heavy metals. In the process of obtaining steels at SC Mechel SA, technological flow was served by Electric steelmaking 2, EBT electric oven with a capacity of 70 tons/hour and Continuous casting plant (in billets) with a maximum capacity of production of 2.5 tons/hour. The activity SC Mechel Targoviste SA was assisted by filtration systems so that the environmental impact to be reduced to a lower limit.
During the elaboration of steel in Electric steelmaking no. 2, total dust are emitted to air, metals (Cd 0.05 mg/Nm3, Pb 0.3 mg/Nm3 and Cr + Cu + Mn + Ni + Zn 5.0 mg/Nm3), organic compounds, nitrogen oxides (NOx), carbon monoxide (CO) and sulphur oxides (SOx) [21]. In addition to these emissions of heavy metal particulates, SC Mechel SA polluted the soil by the waste and slag dumps generated during the metallurgical processes and stored in an open deposit.
Dispersion and transport of pollutants particles according to the pollution direction compass, relative to the most significant pollution source, the furnace of the Electric steelmaking no. 2 belonging to SC Mechel SA
Dispersion of pollutants in the atmosphere largely depends on emission characteristics, meteorological factors, topography, soil roughness, the height of buildings, especially the stack height. Among the meteorological factors, wind direction, intensity, and thereof frequency, are the dominant factors on which we can determine the wind rose indicating the direction of predominant movement of air masses. Based on the wind rose [22] can be designed the pollution direction compass which indicates the direction of dispersion and transport of pollutants particles (Figure 3). In the middle of pollution direction compass is the most significant pollution source, the furnace of the Electric steelmaking no. 2 belonging to SC Mechel SA. East was one of the predominant directions of pollutants transport and the particles have deposited on the ground (agricultural fields) during the process of steel elaboration.
Gray brown luvisol profile (a) and brown-yellowish-rusty upper horizon (b)
In addition to the pollution produced by ground deposition of particles emitted by the SC Mechel SA chimney, these soils are affected by deposit of slag and skim from the same plant. The dumps that are within walking distance (less than 10 m) of agricultural land of residents from Colanu, Romania, are subject to a continuous process of erosion and transport by wind, smaller particles from the surface of stockpiles being transported up to 10 km. Dispersion of the slag particles is due to transport activities to and from the place of storage of metal waste.
Characteristic types of soils for studied area are gray luvisol and gray brown luvisol (Figure 4) according SRTS-2003 (reddish brown after SRCS 1980), soils of a reddish hue, quite evident in the upper horizon and really evident in the middle horizon. Water and air permeability of the soil was moderate. Humus content was about 3%, nutrient supply was moderate, the soil reaction was low-acid with pH values in the range of 6.0 to 6.4, and the degree of base saturation was 80% to 85%.
Bioaccumulation in upper and middle horizon was low; plant debris was mostly decomposed by the action of fungi, and could be observed the formation of small amounts of humus with predominating fulvic acids. Due to intense alteration of mineral component occurs removal of clay colloid from the surface, with accumulation in the Bt horizon, where the profile shows a textural differentiation.
Iron hydroxides
In soils with alluvial B horizon, such as soil in the industrial area of the Targoviste city, colloidal order mineral fraction of this horizon contains large amounts of colloidal hydroxides (e.g. Fe(OH)3 and Al(OH)3) and various hydrated iron and aluminium sesquioxides free-form (mR2O3 nH2O) [23]. Large amounts of iron hydroxides in the humus horizon could be observed for the brown and reddish-brown soils from the industrial zone of Targoviste (Figure 5). The presence of these hydroxides is manifested by brown-yellowish, brown, reddish-brown, yellowish-rusty or rusty lit of the horizon where they are deposited.
Sampling points were chosen to reflect a snapshot of the impact of metallurgical activities in this area by particles emissions. Based on weather conditions and pollution direction compass of Dâmboviţa County (Figure 6), were determined that areas found at SW and W towards the emission source are the most affected. In that location have been chosen the harvest area Zone I – industrial fields, with two subzones, for SW and W directions respectively. Land at NE, E and SE from the source of pollution, are grouped according with the use category in Zone II – agricultural fields sensitive to high concentrations of heavy metals.
Sampling directions from industrial area of Targoviste city according to the pollution rose
Sampling of soil was done at distances between 50 and 1000 meters from the source of pollution, from five different points, chosen according to triangle method. The results of metal concentration represent the average of these five samples. From each sampling point, samples were taken from three layers: the upper layer (0-5 cm depth), middle layer (5-20 cm depth) and lower layer (20-40 cm depth). These layers were chosen according with the depth to which the roots of culture plant normally develop.
The soil samples were processed in the laboratory for elemental analysis by ICP-AES. The soil samples were dried at 40 °C for 24 hours, ground to a fine powder, sieved at 250 µm (according to SR ISO 11464).
Determination of heavy metal concentration in soil was done on replicates samples by Inductively Coupled Plasma - Atomic Emission Spectrometry method (ICP-AES). The soils samples were mineralized in Berghof microwave digester, using a mixture 1:1 with nitric acid (according with Berghof method) prior to ICP-AES analyses. The advantage of ICP-AES is the multielemental detection (Cu, Zn, Sn, Pb, Co, Ni, Mn, Cr and Mo) [24]. For this research, analyses were conducted with Liberty 110 spectrometer of Varian brand. The minimal detection limits of device range according to the analysed element and is 0.4 mg/kg for Zn, Mn and Cu; 0.5 mg/kg for Cr and Co; 0.6 mg/kg for Sn, Ni and Pb. The concentrations values for analysed metals were expressed in milligrams of metal per kilogram of dry soil (mg/kg).
The soil pH was determined with a portable pH-meter, WTW 3110 SET 2, with precision of 0.01 units. For pH analyses, 5 g of each soil sample were mixed with 50 ml KCl 0.1N, F 1000, Tt 0.0056 g/ml and homogenized for 15 minutes with a magnetic stirrer.
In the industrial area of Targoviste city, the concentration of heavy metals in soil was highly dependent on the metal species, the position of sampling point towards the source of pollution, the stack, and the depth of sampling. The general statistical results of heavy metal concentration in studied area are presented in Table 2.
The variation of Cu concentration in the 0-5 cm layer of soil was higher than the variation on the profile. Cu concentration ranged from 578.4 mg/kg in the surface layer, to 170.4 mg/kg (5 -20 cm) and 152.4 mg/kg (20-40 cm). The Cu concentration variation showed that 75% of the samples had values of concentration up to 135.9 mg/kg, and only 25% of the samples had higher concentrations than this value. The same pattern of variation of Cu concentration was followed for the deeper layers. For the layer of 5-20 cm depth, most samples (75%) had concentrations within a narrow range, from 28.7 to 43.6 mg/kg and for the layer of 20-40 cm depth 75% of samples range between 22.0 to 55.2 mg/kg.
The variation of Zn concentration was very high at the surface of soil profile (827.7 mg/kg) and lower in the deeper layers of soil (128.8 mg/kg and 186.9 mg/kg respectively. In all the three studied layers, the concentration of Zn in most of the samples was placed in a very small range as compared to the magnitude of total concentration range. In the surface layer, 50% of the samples showed a concentration of Zn from 42.6 to 86.1 mg/kg and 75% were found between 42.64 to 225.03 mg/kg. The same pattern of distribution of Zn concentration was followed in the deeper layers, 75% of the samples being in a relatively narrow range of concentration from 44.4 to 72.9 mg/kg for the depth of 5-20 cm and 33.1 to 81.8 mg/kg for the layer of 20-40 cm depth.
The values of Sn concentration showed a higher homogeneity in soil when compared to Cu and Zn concentration. Sn concentration ranged from 92.7 mg/kg at the surface of profile to about 40 mg/kg in deeper layers (5-40 cm). The four quadrants of Sn concentration distribution showed narrow values, though there was a concentration of Sn values (50%) in the range 32.7 to 53.9 mg/kg for 0-5 cm layer. In the middle layer (5-20 cm), about 75% of the sample ranged from <LD to 20.9 mg/kg. At 20-40 cm depth, quadrants II and III of the concentration distribution were distributed on the interval from 15.39 to 22.8 mg/kg, the remaining 50% of the samples having values lower or higher than this range.
\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t
\n\t\t\t\t | \n\t\t\t0-5 cm | \n\t\t\t125.5±162.6 | \n\t\t\t22.0-600.4 | \n\t\t\t36.5 | \n\t\t\t30.9 | \n\t\t\t135.9 | \n\t\t\t2.1185 | \n\t\t\t4.6664 | \n\t\t
5-20 cm | \n\t\t\t61.1±55.0 | \n\t\t\t28.7-199.1 | \n\t\t\t35.1 | \n\t\t\t32.5 | \n\t\t\t43.6 | \n\t\t\t1.8284 | \n\t\t\t1.9995 | \n\t\t|
20-40 cm | \n\t\t\t63.3±53.1 | \n\t\t\t22.0-174.5 | \n\t\t\t38.1 | \n\t\t\t35.4 | \n\t\t\t55.2 | \n\t\t\t1.5680 | \n\t\t\t0.7874 | \n\t\t|
\n\t\t\t\t | \n\t\t\t0-5 cm | \n\t\t\t223.9±269.0 | \n\t\t\t42.6-870.3 | \n\t\t\t86.1 | \n\t\t\t73.3 | \n\t\t\t225.0 | \n\t\t\t1.6278 | \n\t\t\t1.3552 | \n\t\t
5-20 cm | \n\t\t\t74.3±42.9 | \n\t\t\t44.4-173.2 | \n\t\t\t54.1 | \n\t\t\t48.4 | \n\t\t\t72.9 | \n\t\t\t1.5888 | \n\t\t\t1.0601 | \n\t\t|
20-40 cm | \n\t\t\t75.6±50.61 | \n\t\t\t33.1-220.1 | \n\t\t\t53.1 | \n\t\t\t49.4 | \n\t\t\t81.8 | \n\t\t\t1.9591 | \n\t\t\t4.0515 | \n\t\t|
\n\t\t\t\t | \n\t\t\t0-5 cm | \n\t\t\t65.1±30.2 | \n\t\t\t32.7-125.4 | \n\t\t\t53.9 | \n\t\t\t41.9 | \n\t\t\t84.8 | \n\t\t\t0.7305 | \n\t\t\t-0.7436 | \n\t\t
5-20 cm | \n\t\t\t12.9±12.9 | \n\t\t\t<LD-44.4 | \n\t\t\t14.9 | \n\t\t\t<LD | \n\t\t\t20.9 | \n\t\t\t0.8094 | \n\t\t\t0.8786 | \n\t\t|
20-40 cm | \n\t\t\t17.8±10.9 | \n\t\t\t<LD-38.2 | \n\t\t\t19.4 | \n\t\t\t15.4 | \n\t\t\t22.8 | \n\t\t\t-0.3501 | \n\t\t\t0.0826 | \n\t\t|
\n\t\t\t\t | \n\t\t\t0-5 cm | \n\t\t\t76.4±98.9 | \n\t\t\t0.6-294.3 | \n\t\t\t43.3 | \n\t\t\t0.66 | \n\t\t\t92.1 | \n\t\t\t1.3987 | \n\t\t\t0.8529 | \n\t\t
5-20 cm | \n\t\t\t47.9±42.6 | \n\t\t\t<LD-121.0 | \n\t\t\t42.5 | \n\t\t\t20.86 | \n\t\t\t64.1 | \n\t\t\t0.7683 | \n\t\t\t-0.5585 | \n\t\t|
20-40 cm | \n\t\t\t34.0±43.6 | \n\t\t\t<LD-145.6 | \n\t\t\t26.3 | \n\t\t\t<LD | \n\t\t\t35.6 | \n\t\t\t1.5800 | \n\t\t\t2.0421 | \n\t\t|
\n\t\t\t\t | \n\t\t\t0-5 cm | \n\t\t\t16.2±4.8 | \n\t\t\t7.1-23.5 | \n\t\t\t17.3 | \n\t\t\t12.9 | \n\t\t\t19.1 | \n\t\t\t-0.5281 | \n\t\t\t-0.4808 | \n\t\t
5-20 cm | \n\t\t\t14.7±5.1 | \n\t\t\t6.7-21.5 | \n\t\t\t13.6 | \n\t\t\t10.3 | \n\t\t\t19.4 | \n\t\t\t-0.0702 | \n\t\t\t-1.6268 | \n\t\t|
20-40 cm | \n\t\t\t13.1±4.0 | \n\t\t\t6.7-19.9 | \n\t\t\t14.9 | \n\t\t\t9.5 | \n\t\t\t15.6 | \n\t\t\t-0.3423 | \n\t\t\t-0.9854 | \n\t\t|
\n\t\t\t\t | \n\t\t\t0-5 cm | \n\t\t\t65.1±58.5 | \n\t\t\t13.8-185.4 | \n\t\t\t37.6 | \n\t\t\t22.0 | \n\t\t\t84.8 | \n\t\t\t1.0999 | \n\t\t\t-0.1291 | \n\t\t
5-20 cm | \n\t\t\t20.2±15.9 | \n\t\t\t8.7-52.7 | \n\t\t\t13.1 | \n\t\t\t12.3 | \n\t\t\t14.8 | \n\t\t\t1.6371 | \n\t\t\t0.8719 | \n\t\t|
20-40 cm | \n\t\t\t23.2±23.9 | \n\t\t\t4.4-72.4 | \n\t\t\t14.2 | \n\t\t\t8.3 | \n\t\t\t17.7 | \n\t\t\t1.5576 | \n\t\t\t0.7595 | \n\t\t|
\n\t\t\t\t | \n\t\t\t0-5 cm | \n\t\t\t1579.7±352.3 | \n\t\t\t1159.9-2348.0 | \n\t\t\t1419.1 | \n\t\t\t1373.2 | \n\t\t\t1731.3 | \n\t\t\t0.9420 | \n\t\t\t0.0714 | \n\t\t
5-20 cm | \n\t\t\t1348.9±243.6 | \n\t\t\t758.9-1677.3 | \n\t\t\t1384.1 | \n\t\t\t1322.7 | \n\t\t\t1504.3 | \n\t\t\t-1.2771 | \n\t\t\t1.5204 | \n\t\t|
20-40 cm | \n\t\t\t1367.5±327.9 | \n\t\t\t720.4-1763.1 | \n\t\t\t1486.3 | \n\t\t\t1258.4 | \n\t\t\t1601.1 | \n\t\t\t-1.0239 | \n\t\t\t-0.1494 | \n\t\t|
\n\t\t\t\t | \n\t\t\t0-5 cm | \n\t\t\t114.6±125.5 | \n\t\t\t13.7-315.6 | \n\t\t\t25.1 | \n\t\t\t21.6 | \n\t\t\t205.7 | \n\t\t\t0.7343 | \n\t\t\t-1.3288 | \n\t\t
5-20 cm | \n\t\t\t46.0±51.7 | \n\t\t\t16.2-168.3 | \n\t\t\t22.7 | \n\t\t\t17.81 | \n\t\t\t30.4 | \n\t\t\t1.7522 | \n\t\t\t1.5205 | \n\t\t|
20-40 cm | \n\t\t\t41.0±52.9 | \n\t\t\t8.2-159.9 | \n\t\t\t18.3 | \n\t\t\t13.8 | \n\t\t\t21.5 | \n\t\t\t1.6981 | \n\t\t\t1.1754 | \n\t\t|
\n\t\t\t\t | \n\t\t\t0-5 cm | \n\t\t\t7.2±7.8 | \n\t\t\t0.6-23.4 | \n\t\t\t4.5 | \n\t\t\t0.6 | \n\t\t\t10.5 | \n\t\t\t1.0334 | \n\t\t\t-0.1858 | \n\t\t
5-20 cm | \n\t\t\t3.0±3.4 | \n\t\t\t<LD-10.8 | \n\t\t\t1.2 | \n\t\t\t0.7 | \n\t\t\t5.1 | \n\t\t\t1.1289 | \n\t\t\t0.2488 | \n\t\t|
20-40 cm | \n\t\t\t2.4±3.3 | \n\t\t\t<LD-9.7 | \n\t\t\t1.0 | \n\t\t\t0.6 | \n\t\t\t1.6 | \n\t\t\t1.6104 | \n\t\t\t0.9883 | \n\t\t|
LD – limit of detection | \n\t\t
Statistical results of heavy metal concentration (mg/kg) in soil surrounding the industrial area of Targoviste city
The variability of Pb concentration was very high, most of the samples showing very low levels, even below the detection limit of the analytical method, in the entire soil profile studied, while some samples presented significant concentrations of Pb up to 294.3 mg/kg (0-5 cm), 121.0 mg/kg (5 to 20 cm deep) and 145.6 mg/kg (20-40 cm). The distribution of the samples in terms of the concentration was varying, 75% of the samples from the surface of soil profile were in the range of concentrations from 0 to 92.1 mg/kg, and the remaining 25% were in the range of 92.1 to 294.3 mg/kg. The Pb distribution was less variable in the deeper layers, the four quadrants of the concentration being distributed at relatively equal intervals, especially for the depth 5-20 cm. Heterogeneity of the sample in terms of the concentration of lead in the ground was indicated by the high value of the standard deviation, higher than the average concentration throughout the studied soil profile.
The concentrations of Co in the samples were distributed homogeneously throughout the range of concentrations for both the upper layer and deeper layers of 5-20 cm and 20-40 cm respectively. The homogeneity of the samples was indicated by the low values of standard deviation, between 29% and 34% of the average, and by the median value that was very close to the average value, 17.3 mg/kg, 13.6 mg/kg, respectively 14.9 mg/kg for the three depths. On the surface of the soil profile, 50% of the analysed samples were in the range of concentration from 12.9 to 19.1 mg/kg.
In surface layer of soil, the range of Ni concentration varied widely, up to 185.4 mg/kg. The soil sample from surface layer presented heterogeneous distribution of Ni, with 75% of the samples from 0-5 cm depth showing a concentration ranging 13.8 to 84.8 mg/kg, and only 25% of the samples ranging 84.8 to 185.4 mg/kg. The Ni concentration variation was lower in deeper layers; most of the samples (75%) were covered by a much narrower range of concentration from 8.7 to 14.8 mg/kg for 5-20 cm depth, and 4.4 to 17.7 mg/kg for 20-40 cm depth.
Distribution of samples within the range of Mn concentration was uniform and 50% of the samples were within the range of 1373.2 to 1731.3 mg/kg, while the remaining 50% of the samples from the surface of the soil profile were higher or lower than this range. The same pattern of samples distribution was followed in the deeper layers, where 50% of the samples were concentrated in the middle of the range of Mn concentration. The standard deviation of the Mn concentration indicates that the samples had similar values of concentration for each layer, accounting 22%, 18% and 24% respectively for the three layers of 0-5 cm, 5-20 cm and 20-40 cm.
The wide variation of Cr concentration in the samples was reflected by the high value of standard deviation, greater than the average concentration for all three depths. Half of the samples from 0-5 cm layer of soil showed Cr concentrations in a very small range between 13.7 and 25.1 mg/kg. The remaining 50% of the samples were distributed in a wider concentration range between 25.1 and 315.6 mg/kg. At depths greater than 5 cm, 75% of the investigated samples had concentrations of Cr in a narrow range of 14.2 mg/kg for the depth of 5-20 cm and 13.3 mg/kg for the depth of 20-40 cm, while the remaining 25% had concentrations in the range of 137.9 mg/kg and 138.4 mg/kg respectively for the two layers of soil.
The range of Mo concentration was higher in the surface of soil profile (22.8 mg/kg) compared to the range of concentration of deeper layers of soil (10.8 mg/kg and 9.7 mg/kg respectively). The majority of samples (75%) showed low levels of Mo, up to 10.5 mg/kg on the surface and 5.1 mg/kg and 1.6 mg/kg in the deeper layers of 5-20 cm and 20-40 cm respectively. The concentration varied greatly, with values of standard deviation higher than the mean concentration.
The horizontal distribution of heavy metals and level of metal pollution in the industrial area of Targoviste city was established by comparing to the Romanian legislation [3], which regulates normal values, alert thresholds and action levels for different trace elements by use of soils, agricultural and industrial land (Table 3).
\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t
\n\t\t\t\t | \n\t\t\t20 | \n\t\t\t100 | \n\t\t\t20 | \n\t\t\t20 | \n\t\t\t15 | \n\t\t\t20 | \n\t\t\t900 | \n\t\t\t30 | \n\t\t\t2 | \n\t\t
\n\t\t\t\t | \n\t\t\t100 | \n\t\t\t300 | \n\t\t\t35 | \n\t\t\t50 | \n\t\t\t30 | \n\t\t\t75 | \n\t\t\t1500 | \n\t\t\t100 | \n\t\t\t5 | \n\t\t
\n\t\t\t\t | \n\t\t\t250 | \n\t\t\t700 | \n\t\t\t100 | \n\t\t\t250 | \n\t\t\t100 | \n\t\t\t200 | \n\t\t\t2000 | \n\t\t\t300 | \n\t\t\t15 | \n\t\t
NV – normal values; ATA – alert threshold for agricultural soil; ATI – alert threshold for industrial soil | \n\t\t
Normal values and alert thresholds of heavy metal concentration (mg/kg) for agricultural and industrial soil in Romania [3]
The concentration of Cu on the surface layer of soil differed greatly between the two studied zones (I and II) (Table 4). Thus, in Zone I, on the SW and W directions towards the emission source, the concentration of Cu reached 401.44 mg/kg and 134.58 mg/kg, values of 7 to 20 times higher than normal levels in this category of soils [25]. In Zone II, the concentrations of Cu on the NE, E and SE directions were slightly greater than the normal value of concentration, ranging between 22.37 and 36.61 mg/kg.
In the case of Zn, the maximum values allowed for industrial soil, 700 mg/kg were overcome on W direction to the source, while the value on SW direction was below that limit, but exceeded the normal value of Zn in soil. The soils in Zone II showed a deficiency of Zn at surface layer and in the deeper layers. In the upper horizon, the Zn concentration was between 46.03 and 86.07 mg/kg, values that are below the normal value of this element in soil [26].
\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t||||||||||
\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t|||||||
\n\t\t\t\t | \n\t\t\t401.44 | \n\t\t\t134.58 | \n\t\t\t32.41 | \n\t\t\t22.37 | \n\t\t\t36.61 | \n\t\t||||||
\n\t\t\t\t | \n\t\t\t194.28 | \n\t\t\t719.13 | \n\t\t\t74.45 | \n\t\t\t46.03 | \n\t\t\t86.07 | \n\t\t||||||
\n\t\t\t\t | \n\t\t\t112.31 | \n\t\t\t52.79 | \n\t\t\t43.78 | \n\t\t\t33.77 | \n\t\t\t82.90 | \n\t\t||||||
\n\t\t\t\t | \n\t\t\t85.38 | \n\t\t\t252.00 | \n\t\t\t0.60 | \n\t\t\t0.76 | \n\t\t\t43.25 | \n\t\t||||||
\n\t\t\t\t | \n\t\t\t20.42 | \n\t\t\t19.93 | \n\t\t\t14.11 | \n\t\t\t8.94 | \n\t\t\t17.48 | \n\t\t||||||
\n\t\t\t\t | \n\t\t\t166.64 | \n\t\t\t83.84 | \n\t\t\t15.01 | \n\t\t\t22.42 | \n\t\t\t37.39 | \n\t\t||||||
\n\t\t\t\t | \n\t\t\t1264.26 | \n\t\t\t2156.48 | \n\t\t\t1726.44 | \n\t\t\t1362.45 | \n\t\t\t1388.85 | \n\t\t||||||
\n\t\t\t\t | \n\t\t\t200.31 | \n\t\t\t312.33 | \n\t\t\t13.88 | \n\t\t\t24.98 | \n\t\t\t21.68 | \n\t\t||||||
\n\t\t\t\t | \n\t\t\t9.79 | \n\t\t\t0.6 | \n\t\t\t20.57 | \n\t\t\t0.65 | \n\t\t\t4.45 | \n\t\t||||||
\n\t\t\t | Under normal limit | \n\t\t\tExceed normal limit | \n\t\t\tExceed the alert threshold for agricultural soil | \n\t\t\tExceed the alert threshold for industrial soil | \n\t\t
Horizontal distribution of heavy metal concentrations (mg/kg) in the industrial area of Târgovişte city
Sn concentrations in the analysed soils were above normal values (Table 4) in both the Zone I and Zone II. A concentration of about 6 times the normal limit was found in soils under the SW direction. For other samples, the concentration of Sn in soil ranged from 33.77 to 82.90 mg/kg, the lowest value being on E direction and the highest on SE direction.
Although the normal value of Pb in soil is 20 mg/kg, the concentration of this element in the studied samples of soils did not exceed the threshold. The soil in Zone II showed the lowest concentration. In the SE direction, Pb concentration in soil was the highest, 43.35 mg/kg. The soil in the Zone I, showed values of Pb concentration that exceeded 4 to 12 times the normal values: 85.38 mg/kg in the SW direction and 252.00 mg/kg on the W direction.
The concentrations of Co in soils were not much higher than the normal values of metal concentration in soil. Higher values were found in the soil from Zone I, 19.93 mg/kg in the W direction and 20.42 mg/kg in the SW direction. The soils in the Zone II showed values of Co concentrations that varied between 8.94 and 17.48 mg/kg. The lowest value was on E direction, and the highest value on SE direction.
The concentration of Ni in soils varied widely in the two studied zones. In Zone I, the concentration of Ni was between 4 and 8 times higher than the normal value of metal concentration in soil, 83.84 mg/kg in the W direction and 166.64 mg/kg on the SW direction. The soil in Zone II showed Ni concentration close to normal values, ranging from 15.01 to 37.39 mg/kg. The highest value was for the Ni concentration on SE direction.
Concentration of Mn in the soil was two times higher than the normal value and range between 1264.26 mg/kg and 2156.48 mg/kg. The lowest value of Mn concentration was on SW direction and the higher on the W direction.
Concentrations of Cr in soils from the industrial area were very different between the two studied zones. In Zone I, the concentrations were extremely high compared to the normal limit (30 mg/kg), reaching values over 10 times higher: 200.33 mg/kg and 312.33 mg/kg on SW and W directions respectively. In Zone II, Cr concentration showed values below the normal concentration of Cr in this type of soil, and varied between 13.88 and 24.98 mg/kg [27].
Molybdenum concentration in the surface layer of soil varied within wide limits, irrespective of the position towards the source of pollution. In Zone I, concentration of Mo has the minimum value in the W direction (0.6 mg/kg), and the maximum value in the SW direction (9.79 mg/kg). This value was about 5 times higher than the normal value of Mo concentration in soil. In Zone II, the concentration of this metal varied also within wide limits, from 0.65 mg/kg in the E direction to 20.57 mg/kg in the NE direction. The recorded values were more than 10 times higher than normal values.
The vertical distribution of heavy metals in the soil profile (0 – 40 cm) is shown in figures 7 – 14, which indicates the level of heavy metals in the three soil layers: 0 – 5 cm, 5 – 20 cm and 20 – 40 cm. For each layer, linear regression was calculated to indicate correlations of heavy metal concentrations with the pH.
The high concentrations of Cu in the SW direction were maintained at very high level in the depth of soil profile (Figure 7). In the W direction, Cu concentration decrease to depth of 40 cm to levels of 27 mg/kg. The soil in Zone II showed similar values of Cu concentration on the entire profile of soil. Between the Cu concentration and the pH of soil was observed a moderate correlation in the surface layer of soil (0.3) and very low correlations for the two deeper layers. All the correlations were positive.
Extremely high Zn concentration from the surface layer of soil did not maintained in depth. Below 5 cm depth the concentration of Zn decreased to values lower than 35 mg/kg (Figure 8). In the SW direction, the concentration of Zn in the deeper layers of soil remained at levels comparable to the surface layer, ranging between 154.38 and 194.28 mg/kg. The lowest values were in the middle of the soil profile, and the highest values on surface layer. The design of the Zn distribution in soil was maintained in Zone II. The highest concentrations were on the surface, decreased in the middle of soil profile, and increased in the lower part of the profile. The concentrations of Zn to this area were between 46.03 and 86.07 mg/kg. Correlation between the Zn concentrations in the soil with its pH is strong in the upper layer (0.48), and very low to depth.
Copper vertical distribution in soil and correlation with pH
Zinc vertical distribution in soil and correlation with pH
In contrast to Cu and Zn, Sn distribution in the soil profile showed a very wide variance (Figure 9). The surface layer showed Sn concentration much higher than in depth. For all studied direction, was observed that the concentration of Sn decreased towards the centre, and grow on the bottom of the profile. Correlation between the Sn concentrations and the pH of soil is positive, but to a different extent, depending on the depth. Thus, the surface layer had a very low correlation, in the 5-20 cm layer the correlation was low, and the bottom of soil profile the correlation was moderate (> 0.4).
Distribution of Pb in the soil did not follow a pattern, but varied from one area to another. Thus, the high Pb concentration from the surface, in the W direction, decreased sharply towards the middle of soil profile, and continues to decrease to the bottom of the profile (Figure 10). In the SW and E directions, the Pb concentration was higher in the middle and lower soil profile than in the upper horizon, far exceeding the normal value of Pb concentration in soil. In the NE and SE directions, Pb concentrations were similar throughout the entire soil profile. The correlation between the Pb concentrations in soil and the pH decreased from the surface to the depth of soil profile. The correlation was moderate positive in the upper layer (0.47), and low but positive to the bottom of soil profile.
Tin vertical distribution in soil and correlation with pH
Lead vertical distribution in soil and correlation with pH
The distribution of Co on the soil profile varied from one point to another (Figure 11). In the SW, SE and E directions, the Co concentration in the soil increased slightly in the middle of soil profile and decreased sharply towards the bottom of it. In the W direction, the Co concentration decreased sharply towards the centre of soil profile and continues to decrease to the bottom thereof. In the NE direction, the Co concentration is higher in the lower part of the profile as compared to the upper layers. The correlation between the Co concentrations in soil and pH varied on the soil profile as intensity. In the upper layers, the correlation is positive, but very low (<0.2), while the lower layers showed weak negative correlation (0.2 - 0.4).
Cobalt vertical distribution in soil and correlation with pH
Nickel concentration varied along the profile of soil. Much higher values were observed in the surface layer of soil compared to the values representing the concentration of Ni in the middle of the profile. At the bottom of the profile, the concentrations increased slightly (Figure 12). For soil samples collected in the SW direction, the metal concentrations maintained at high value on the entire soil profile compared to other directions. In the W direction, the surface layer showed much higher concentrations of Ni, and in the deeper layers the value of Ni concentration were still high. The correlation between the Ni concentrations in soil and the pH was low, positive and decreased in intensity with the depth profile.
Except for samples collected west from the pollution source, distribution of Mn was approximately uniform throughout the soil profile, the concentration ranging between 942.32 mg/kg and 1578.64 mg/kg at 5-20 cm depth, and between 796.68 and 1631.13 mg/kg at 20-40 cm depth (Figure 13). The surface layer showed a low correlation between the Mn concentrations and pH, in the 5-20 cm layer the correlation was strong (> 0.6) and in the lower part of the soil profile correlation was moderate.
Nickel vertical distribution in soil and correlation with pH
Manganese vertical distribution in soil and correlation with pH
The soils in Zone II showed similar values of Cr concentration on the entire soil profile, observing only a slight increase in the median layer (Figure 14). In the SW and W directions, Cr distribution differed on the soil profile. In the surface layer the concentration had high values, but they decreased with the depth. Only in the surface layer the concentration of Cr in the soil had a strong correlation with pH of soil (> 0.6).
The Mo concentration varied widely in depth of soil profile (Figure 15). In the SW, NE and SE directions the concentrations decreased significantly in the middle of the profile and remain at the same value at the bottom of it. In the W direction, a higher concentration of Mo (4.94 mg/kg) was found at a depth of 5-20 cm. The best correlation between the Mo concentration in soil and pH was at depth of 5-20 cm, with values > 0.4. The upper and lower layers had a lower correlation between Mo concentration and pH.
Chromium vertical distribution in soil and correlation with pH
Molybdenum vertical distribution in soil and correlation with pH
The statistical analysis indicated that the heavy metal concentration in soil is negatively correlated with the depth, as the metal concentration decreased with the increasing of depth (Table 5). The correlation was statistically significant at level lower than 5%. Heavy metal concentration in soil was positively correlated with the pH of soil, with low to moderate intensity, except the Mn concentration which showed a very low negative concentration.
\n\t\t\t | \n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t
\n\t\t\t\t | \n\t\t\t-0.2454 a\n\t\t\t | \n\t\t\t-0.3469 a\n\t\t\t | \n\t\t\t-0.5965 a\n\t\t\t | \n\t\t\t-0.2588 a\n\t\t\t | \n\t\t\t-0.2907 a\n\t\t\t | \n\t\t\t-0.3879 a\n\t\t\t | \n\t\t\t-0.2639 c\n\t\t\t | \n\t\t\t-0.3277 a\n\t\t\t | \n\t\t\t-0.3469 c\n\t\t\t | \n\t\t
\n\t\t\t\t | \n\t\t\t0.3796a\n\t\t\t | \n\t\t\t0.4171 a\n\t\t\t | \n\t\t\t0.1554 b\n\t\t\t | \n\t\t\t0.5066 a\n\t\t\t | \n\t\t\t0.5675 c\n\t\t\t | \n\t\t\t0.3991 a\n\t\t\t | \n\t\t\t-0.0995 c\n\t\t\t | \n\t\t\t0.5007 a\n\t\t\t | \n\t\t\t0.0932 a\n\t\t\t | \n\t\t
ª - p < 0.05; b - p < 0.01; c - p < 0.001 | \n\t\t
Pearson coefficient of correlation between heavy metal concentrations in soil and depth and pH of soil
The vertical mobility index (VMI) represents the relative explanation of heavy metal concentration between two underlying layer of soil: between 0-5 cm and 5-20 cm; between 5-20 cm and 20-40 cm (Figure 16). The metal mobility between layers was statistically significant at 95% confidence level. VMI will indicate a very weak mobility of metal at values lower than 20%, weak mobility of metal at values between 20 and 40%, moderate mobility of metal at values between 40 and 60%, strong mobility at values between 60 and 80%, and very strong mobility at values higher than 80%.
Distribution of Cu in the soil profile was given by the very strong correlation of the concentration of this element in the three layers of soil profile. High values of vertical mobility index were observed between the concentrations of Cu in the two underlying layers, which demonstrated the very high mobility of Cu in the soil, mobility influenced also by the pH. Values of correlation between concentrations at different depths indicated weak Zn mobility on the soil profile to depth of 20 cm and a very strong mobility between 20 and 40 cm.
Vertical mobility index (VMI) of heavy metals between the layers of the soil profile, statistically significant at 95% confidence level
The mobility index of Sn was different depending on the depth. In the surface layer, this metal had a weak mobility; the correlation between the two layers (0-5cm and 5-20 cm) was very low. At greater depths, Sn mobility index was higher, indicated by the strong correlation of the concentrations at depths greater than 20 cm. Correlation of Pb concentration between layer of 0-5 cm and the other two layers was very low (<0.3). A strong correlation exists only between 5-20 cm and 20-40 cm depth which indicate a very strong mobility of Pb. The correlation between the concentrations of Co in the soil profile indicated a strong mobility of metal between the surface layer and underlying layers. The correlation between the Ni concentrations of different depths of soil profile is very strong, indicating a very strong mobility of Ni in soil which increased with depth.
The correlation between the concentrations of Mn in different depths of the soil profile is very strong, which indicated that a significant increase in the concentration of Mn in the upper layer will lead to an increase of Mn concentration also in the depth due to very strong mobility of this metal. The correlation between the concentrations of Cr in different depths of soil profile indicated a weak mobility of Cr between the surface layer and the middle layer of soil profile and a very strong mobility in the lower part of the soil profile. Correlations between the Mo concentrations were different on the soil profile: very weak in its upper layer and strong in the lower layers of soil profile.
Because of the metallurgical activities carried out in the vicinity of Targoviste, which produced in time significant amounts of particulate matter with a high content of Pb, Cr, Cu, Mn, Ni and Zn, the quality of agricultural soils is negatively influenced by the concentrations of heavy metals, which represent a risk of toxicity to humans. In order to evaluate the degree of loading of soils with heavy metals, the present study shows: (i) the horizontal distribution of heavy metals, depending on the prevailing direction of the air masses movement (wind rose) and (ii) vertical distribution to highlight the mobility of heavy metals into the soil profile, depending on the depth to which the plant roots can be found [15].
Previous studies have shown Targoviste area as an area of potential risk of heavy metal toxicity, along with other sources of pollution in Romania, as Copşa Mică, Deva and Baia Mare. This study presents the results of the concentration of heavy metals in soils near Targoviste, and are considered the high risk toxic metals such as Cu, Zn, Sn, Pb, Co, Ni, Mn, Cr, Mo. The analysis of horizontal distribution of heavy metals (Table 4) indicated that the agricultural soil in the vicinity of metallurgical unit were loaded with heavy metals concentrations exceeding several times the normal values and even alert threshold. Some values indicated concentrations of Cu and Zn even higher than in Copşa Mică [16] and Baia Mare [17].
Soils most affected by heavy metal pollution were those located on SV and V directions against the source of pollution, which are the predominant direction of air masses movement in the studied area. Also the other studied directions are characterized by concentration of heavy metals higher than normal limits, constituting a potential risk in the use of those soils in agriculture.
Analysis of vertical distribution of heavy metals indicated that high levels of heavy metals are caused primarily by industrial activity and less by the concentration of metals in the parent material. The concentration of all metals was higher in surface layer of soil (0-5 cm) because of deposition of particulate matter [21] and lower in the deeper layers of soil, possibly due to binding of metals to soil organic fractions (in the surface layer) that have slowed the metal mobility on the profile and decreased the transfer of metals to the underlying layers. Statistical analysis of correlations between the metal concentrations in soil and depth of the soil layer showed a negative correlation, which confirmed the hypothesis that the high concentration of heavy metals in soils from the industrial area of Targoviste, comes from a source of pollution and not from the parent material.
The metal mobility from the surface layers to the deeper layers can be explained on the basis of vertical distribution pattern of heavy metal. In order to measure the metal mobility on the profile of soil, a vertical mobility index (VMI) was calculated. This index indicated the extent to which that metal from a top layer of soil was transferred to the deeper layer by leaching and adsorption to soil particles. Depending on the type of soil, the mobility varies, promoting or inhibiting the rate of metal transfer from surface soil to groundwater, where the toxicity hazard is more difficult to control and the remediation actions are trickier. The most mobile heavy metals in investigated soils were Cu and Ni, with a mobility of 94 % and 89 % respectively, between the two layers from the surface of soil profile and a mobility of 98 % and 97 % respectively, between the two deeper layers. The hazard risk of these two metals to get into the groundwater was expressed by the high values of VMI. Also Mn and Co showed quite high values of VMI, which placed them as potential hazardous metals. Analysis of heavy metal mobility is important because once they reached the groundwater they present a greater risk to humans. Long-term exposure to high concentrations of these metals can cause serious illnesses in humans [4, 10, 11], and the intervention for remediation of soil is urgent, before the heavy metals will reach the groundwater.
Following chemical analysis by ICP-AES, we found the heavy metal concentration levels above the normal value of an industrial soil, and sometimes even exceeding the alert limit (according to Order 756/1997).
Distribution of heavy metals on soil profile showed that accumulation of metal in the soil decreases with the depth. The concentrations were higher on the surface of the soil profile. This indicates a continuous impact of metallurgical activities on soil by accumulating new quantities of metals.
The concentration of heavy metals in soil was also considered to be in connection with the pH and chemical composition of soil: the presence or absence of other metallic elements.
The vertical mobility index indicated moderate to strong mobility of majority of studied metals, especially in the lower layer of the soil profile, 20-40 cm.
The research is part of the PhD thesis “Studies and research concerning the remediation of heavy metal polluted soil by eco-technological procedure”, in Romanian, realized by the author in 2011. Is a good opportunity to thank my colleagues Sorin Ciulei for his support in soil assessment and evaluation, Irina Fierascu and Radu Claudiu Fierascu for their support in the sample analyses by ICP-AES. Also I want to thank my thesis coordinator, Prof. Georghe Ionita for guidance in preparing the thesis and to Prof. Dumitru Ion for the financial support for the publication.
Shoulder surgery by arthroscopy or open methods has increased in recent years. The choice of anesthetic technique depends on the patient’s conditions, the preferences of the surgical group, the position the patient is to be placed, and the experience of the anesthesiologist. General anesthesia (GA) has been considered the ideal technique for this type of surgery, but advances in regional anesthesia have gradually changed this statement. The approaches, interscalene (ISBP) block (C5 C6) or the upper trunk (UT) are the most established options; the supraclavicular approach offers optimal coverage, including the proximal arm. Patients with respiratory compromise may not tolerate hemi diaphragmatic paresis (HDP) associated with proximal approaches. Distal approaches are associated with lower rates of HDP, but coverage of the proximal upper extremity may be incomplete. The use of ultrasound guidance (USG) for nerve blocks has increased success and safety and has allowed access to more peripheral brachial plexus blocks to prevent diaphragmatic paralysis. Regional anesthesia is also an excellent supplement to GA to improve postoperative pain management and decrease the need for opioid use.
Clavicle surgery has even more controversy about the choice of the regional block, since the innervation has not been well described. But in recent years, alternative regional block methods to interscalene brachial plexus block have appeared that are suitable as single anesthesia or combined with sedation or GA.
In this chapter, we pretend to describe the innervation of the shoulder and clavicle based on current knowledge and the sonoanatomy of the neck and armpit as a guide for the performance of regional nerve blocks.
Since shoulder surgeries produce severe postoperative pain, regional anesthesia techniques could effectively control pain at rest and in motion, reduce muscle spasm and facilitate early discharge [1].
The BP is formed by the fusion of the ventral ramus of the spinal nerves C5, C6, C7, C8, and T1, with the variable contribution of C4 (15-62% of cases) and T2 (16-73% of cases). The roots emerge in the groove between the anterior scalenus and middle scalenus muscles [2]. Shoulder and proximal arm innervation are provided by branches of the BP: suprascapular nerve (SSN) (from posterior division of UT), axillary and subscapular nerves (from posterior cord), lateral pectoral nerve, and medial brachial cutaneous nerve (MBCN)) (from lateral cord), and the intercostobrachial nerve (ICBN) (originating directly from proximal intercostal nerves). SSN may be spared by an infraclavicular approach (Figure 1) [3, 4].
Brachial plexus. Roots – Start in the spinal cord. Arise from anterior rami C5-T1. Landmark: Pass inferolateral between the anterior and middle scalene muscles. Trunks
The most frequently identified innervation pattern comprises three nerve bridges consisting of articular branches from suprascapular, axillary, and lateral pectoral nerves, connecting trigger points (Figures 2 and 3) [5, 6, 7].
Distribution of shoulder articular branches. Courtesy of MF Rojas.
Shoulder structures and their related innervation.
Articular branches classified in relation to the spinoglenoid notch:
Medial branch (MSAb) originates 1.3 cm proximal to the suprascapular notch, giving branches to the coracoclavicular ligaments and the medial pole of the subacromial bursa, clavicular insertion of the acromioclavicular ligament, and motor branches to the supraspinatus muscle.
Lateral branch (LSAb) originates at the level of the suprascapular notch, giving sensory branches to the lateral subacromial pole and acromial insertion of the acromioclavicular ligament. Two subacromial branches provide medial and lateral sensory innervation (bipolar) to the subacromial bursa.
The posterior glenohumeral branch (PGHb) originates at 3 cm from the suprascapular notch, and posterior to the spinoglenoid ligament, course inferomedial towards the posterior capsule of the shoulder [8].
One or two articular branches of the main trunk travel with the anterior humeral circumflex artery between the tendons of the subscapular and latissimus dorsi muscles branching into medial branch to scapular aspect of the anteroinferior capsule and portions of the axillary recess; lateral branch to humeral portion of the anterior capsule [6]. The posterior division (after leaving the quadrangular space) gives a branch for the teres minor muscle, from which emerge 1 to 4 articular branches, to innervate the posteroinferior capsule. The branch innervating the deltoid muscle gives small multiple articular branches towards the lateral aspect of the humeral head the posterior and lateral supra-lying fascia of the shoulder capsule [6, 9, 10].
The LPN arises from two branches of the anterior divisions of the upper and middle trunks (33.8% of cases), or as a single root of the lateral cord (23.4%). It receives fibers from C5 to C7. Cross the superomedial side of the coracoid process and sends small branches to the coracoclavicular and coracoacromial ligaments, anterior acromioclavicular joint, subacromial bursa and anterosuperior portion of the glenohumeral capsule. It gives branches to the periosteum of the clavicle. Therefore, its blockade produces analgesia for distal clavicle surgery [6, 11]. The muscular branch originates from the articular branch of the LPN and innervates the deltoid muscle and skin over the subacromial region (Figure 4) [7, 11].
Lateral pectoral nerve.
A glenohumeral articular branch anastomosis with branches of the AN to innervate the long head of the biceps tendon (LHBT) and anterior capsule. The superior subscapular nerve gives 1 or 2 articular branches to innervate the anterosuperior quadrant of the glenohumeral joint [12]. Receives fibers for C5-C6.
The
Mechanoreceptors are more concentrated in the medial and lateral insertions of the anterior capsule. Nociceptors are identified primarily in the upper quadrant of the shoulder, including the subacromial bursa (SAB), glenohumeral ligaments (GHL), coracoacromial (CAL), coracoclavicular ligaments (CCL), the proximal portion of the LHBT, and the transverse humeral ligament (THL). The SAB is the area of densest and tripolar nociceptive innervation. These three nociceptive poles may correspond to the location of the lateral/medial subacromial branches of the SSN (i.e., lateral and middle poles) and the articular branch of the lateral pectoral nerve LPN (anterior pole); Thin articular branches of the AN may also participate in the innervation of the lateral pole of SAB [6].
The most painful structures in clavicle surgery include the skin over the incision area and the highly innervated periosteum. The supraclavicular nerve originates as a single trunk from the anterior ramus of cervical nerves C3-C4. It divides into medial (suprasternal), intermediate (supraclavicular), and lateral (supra-acromial) branches. The medial branch supplements the skin over the anterior aspect of the thorax, as far below as the second rib, and the sternoclavicular joint. The intermediate branch pierces the deep cervical fascia just above the clavicle and runs over the pectoralis major and deltoid muscle; supply cutaneous innervation to the skin above these muscles, as far below as the second rib. The lateral branch pierces the deep cervical fascia just above the clavicle, passes over the acromial process, to innervate skin of the upper and posterior shoulder regions (Figure 5) [13, 14].
Nerves involved in clavicular innervation.
Innervation of the clavicle itself is less well described. Different authors attribute contributions from SSN, long thoracic, nerve for the subclavian muscle, and LPN [15].
Situated posterior to the clavicular part of the pectoralis major muscle. It extends from the clavicle, costochondral joints, and coracoid process. It converges in the axilla and acts as a protective structure over the neurovascular package. The clavicular fascia splits to enclose the subclavius muscle before attaching to the clavicle, the posterior layer fuses with the deep cervical fascia which connects the omohyoid muscle to the clavicle. Medially, it is attached to the first rib before coming together with the fascia over the first two intercostal spaces. Laterally, it is attached to the coracoid process before blending with the coracoclavicular ligament. The fascia often thickens to form the costocoracoid ligament, between the first rib and coracoid process. Inferiorly, the fascia becomes thin, splits around pectoralis minor, and descends to blend with the axillary fascia and laterally with the fascia over the short head of the biceps. It is pierced by CALL [cephalic vein, artery (thoracoacromial), lateral pectoral nerve, lymphatics]. The clavipectoral fascia surrounds the clavicle, and the nerve endings of the clavicle penetrate this fascia (Figure 6) [16].
Clavipectoral fascia.
Interscalene or supraclavicular block of the BP are considered the standard technique for anesthesia and analgesia in this type of surgery. The most common adverse effect is HDP due to ipsilateral PN block in 100% of patients and a 27% decrease in forced vital capacity and forced expiratory volume at the first second [17]. At the level of the cricoid cartilage (C6 transverse process (TP)) the PN is 0.18 cm prior to the BP, but it diverges at a rate of 3 mm for each centimeter below the cricoid cartilage.
USG has allowed to decrease the anesthetic minimum volume required in 50% of patients (5-7 mL vs. 30-40 mL) using ropivacaine 0.75% or bupivacaine 0.5%, and a decrease of 50% in the incidence of paralysis of the diaphragm when the injection is performed laterally to the C5-C6 roots. If the concentration of the anesthetic is also diluted to a half or third, the HDP rate is reduced to 20% (it is still a contraindication in patients with decreased lung reserve) but carries the risk of not achieving surgical anesthesia and decreasing the duration of the blockade. According to Renes et al., if the injection is done at the C7 root level, the minimum volume required to block C5-C6 in 50% of patients was 2.9 mL (maximum volume of 6 mL), with no PN block (although there is a substantial risk of vascular lesions from punctures at this level). Renes et al. avoided PN block by administering the anesthetic in the “cornet pocket “ (intersection of the first rib with the subclavian artery and posterolateral aspect of the BP) and a volume less than 20 ml [18]. Aliste et al. compared ISB with supraclavicular block following the Renes technique, finding equal pain control, but with HDP rate of 9% [19]. Cornish found a 1% of HDP rate by advancing a catheter from the supraclavicular level and locating the tip at the infraclavicular level, inferomedial to the coracoid process [20, 21].
A combination that could be effective would be the association of a SSN block with a BP block at infraclavicular level [22] (addresses the axillary, lateral pectoral, subscapular nerves), although Petrar et al. [23] reported a 3% incidence of HDP during infraclavicular BP block (30 mL ropivacaine 0.5%).
The following paragraphs describe different techniques to achieve a selective block of the nerves supplying the shoulder.
It focuses on the anesthetic deposit near the UT, before the take of the SSN. At this level, the phrenic nerve (PN) has diverged from the BP. Compoy et al. [24] found that 5 mL of methylene blue injected around UT stains SSN, lateral pectoral nerve, and roots of C5 and C6, but not of the PN [25]. Kim et al. found analgesic equivalence between UT block and ISB, achieving equivalent surgical anesthesia and HDP incidence of 5% vs. 71% using 15 mL of injectate [26]. Ultrasound (US) examination reveals the plexus in the groove between the anterior and middle scalene muscles, deep to the prevertebral fascia. The sternocleidomastoid muscle (SCM) lies superficially, and the PN can be seen on the anterior surface of the anterior scalene muscle (ASM), crossing it towards the medial side, after the last contribution originating in the C5 root. Sonoanatomy of the transverse processes can be used to identify spinal roots. Serial images reveal the process of confirmation of the UT [27].
The blocking needle is advanced from lateral to medial, under the deep cervical fascia until its tip reaches the UT lateral edge, proximal to the exit of the SSN (it is identified as a rounded hypoechoic structure that separates laterally from the UT and runs deep to the omohyoid muscle). The needle does not pass through the middle scalene muscle (MSM), where the dorsal scapular nerve (DSN) and long thoracic nerve (LTN) are located. The injectate volume is 7 to 12 mL of local anesthetic (LA) (one-half or one-third strength). Here the nerves have a greater amount of perineural tissue, protecting against neurological dysfunction, which has been reported in about 14% of ISBP blocks and can last for up to 10 days (Figure 7).
Upper trunk and supraclavicular nerves blockade. A. C5 and C6 (bifid) roots at interscalene space, near to PN. C7 TP view. B. UT formation (inferior to C7 TP). C. Origin of supraescapular nerve (SSN). D. Back to UT - needle at its posterior surface. Local anesthetic (LA) injection at posterior surface of UT. E. Retreated needle to space between SCM-MSM. LA injected around supraclavicular nerves.
The UT provides anesthesia to nerves from the spinal cord segments C5 and C6 (originating fiber to SSN and AN, inferior subscapular nerve, and partially, to LPN) [25] and decreases the incidence and severity of PN block. HDP was observed in 97.5% in ISB vs. 76.3% of the UT block groups (P = 0.006); paresis was complete in 72.5% vs. 5.3% of the patients, respectively. The decrease in spirometry values from baseline was significantly greater in the ISB block group. UT block provides non inferior analgesia compared to ISBP block [28].
It can be supplemented with blockade of the supraclavicular nerves to anesthetize the skin over the shoulder. The needle is retracted to the space between prevertebral fascia (over the MSM) and superficial (enveloping) layer of the deep cervical fascia, under the SCM, where the supraclavicular nerves are located. A new injection of 2 to 3 mL of LA blocks nerves supplying skin over collarbone and shoulder cap and their sensitive contribution to the acromioclavicular joint.
The supraclavicular nerve trunk (C3 and C4) emerges at the posterior edge of SCM. The superficial cervical plexus (SCP) is localized by placing a transducer on the posterior edge of the SCM at the level of the upper pole of the thyroid cartilage. It can be difficult to identify the individual nerves. The greater auricular nerve (GAN) is a useful reference reliably identified as a small superficial hypoechoic round structure on SCM (Figure 8) [29].
Supraclavicular nerve trunk and SCP scan process.
The posterior approach in the suprascapular fossa (in the space between the suprascapular notch and the spinoglenoid notch) where the nerve travels through its floor under the supraspinatus muscle fascia, results in adequate flooding of SSN with minimal propagation to the BP [30] but may spare MSAb. This approach is inferior to ISBP block for pain control, at least in the first 4 hours [31, 32, 33]. The UT (C5-C6) is the major contributor to the suprascapular, axillary, and subscapular nerves. Hence, UT blockade can provide adequate control of shoulder pain, but it is still remarkably close to the PN [34, 35].
With ultrasound image, the SSN could be identified as it branches from UT, and runs laterodorsally underneath the omohyoid muscle, in 81% of cases vs. 36% in the supraspinatus fossa, at an average depth of 8 mm vs. 35 mm in the supraspinatus fossa. Peripheral nerve stimulator can help in the identification [35]. Rothe et al. studied twelve healthy volunteers; the SSN was followed into the subclavian triangle under the inferior belly of the omohyoid muscle; injecting 1 mL of lidocaine 2%, 10 blocks were performed, 8 demonstrated a reduced manual muscle-testing scale (MMT) of the supra- and infraspinatus muscles at 15 min and 30 min; increasing the injected volume, produced musculocutaneous and radial nerves blockade due to cephalic diffusion of the anesthetic (Figure 9) [36].
Scan sequence of the SSN at the supraclavicular fossa. A: Locate the transverse process of C6 vertebral vertebra and C6 and C5 roots. B: Scanning downward, locate the C7 TP and C7 root, which can be seen laterally to vertebral vessels. C: Just below the C7 transverse process, C7 root runs towards the interscalene groove. The PN is diverging from the BP, on the anterior surface ASM. Caudally to the C7 transverse process, UT and MT conformation can be imaged. D: In the supraclavicular fossa. From the UT branches the SSN. E: The SSN travels below the omohyoid muscle. F: The SSN separates from the UT, below omohyoid muscle. The nerve goes along suprascapular artery.
In 14 BP of 7 corpses, the separation between the SSN and the PN was found to be 2.5-6.4 cm, and the injection of 10 mL of solution around the SSN produced staining of the UT of the BP and its branches (SSN, anterior and posterior divisions - 14 cases, 100%), the middle trunk (MT) (13 cases, 93%), the PN (3 cases; 21.4%) [37]. In the cadaveric study by Sehmbi, the SSN and omohyoid muscle were easily identified and, with nerve injections of 5 mL, nerve staining with contrast dye was seen in 90% of dissections. The UT, MT, and LT were stained in 90%, 80% in 20% of dissections, respectively. The PN was mildly stained in 20% of the dissections [38]. Figure 9 shows the scan sequence of the SSN at the supraclavicular fossa.
The articular branch or LPN crosses the superomedial side of the coracoid process [6, 11]. The US probe is placed between the inferior border of the clavicle and the superior border of the coracoid process. Below the deltoid muscle, the acromial branch of the thoracoacromial artery and, along with it, the nerve can be found (Figure 10).
USG to locate the articular branch of LPN.
The AN provides motor innervation to subscapular, teres major and minor, and deltoids muscles. The nerve branches before entering the quadrangular space. The anterior division of the AN originates the first articular branch, which ends in the anteroinferior capsule; blocking the nerve by the posterior approach can provide incomplete analgesia.
The sensitive skin supply of the medial aspect of the arm is provided by MBCN, ICBN, and variable branches of the intercostal nerves [39].
The AN run into the inferolateral margin of the subscapular muscle and enters the quadrangular space (QS) (limits: upper, teres minor muscle; inferior, teres major muscle; medial, long head of the triceps muscle; lateral, surgical neck of the humerus; anterior, insertion of the subscapular muscle on the minor tuberosity). The subscapular muscle, the upper edge of the teres major muscle, and the humerus are the sonographic marks that lead to the identification of the AN. The ICBN originates mainly from the second intercostal nerve, with variable contributions from intercostal nerves T1, T3, and T4. It is identified in the axillary subfascial space, along.
with fat, lymph nodes, and other cutaneous branches of the upper intercostal nerves. After crossing the axillary subfascial space, it courses on the surface of the latissimus dorse muscle, covered by the superficial axillaryfascia [40].
With the arm abducted 90o, the BP is identified in the armpit (anterior to the teres major and the tendon of the latissimus dorse muscles, seen in short axis) (Position 1, Figure 11). The probe moves slightly in a proximal direction (position 2, Figure 11) towards the QS, which is identified as soon as the upper edge of the teres major muscle deepens. At this point, the AN appears as an oval honeycomb structure, accompanied by the posterior circumflex artery of the humerus (although it has an inconsistent course and presence). The elevation of the arm from 90 o to 180 o brings the nerve closest to the skin by closing the quadrangular space.
AN US images at axillary fossa. A. Transducer position 1. The US imagen corresponds to D. B. Transducer position 2. The US imagen corresponds to E. C. Anterior view of axilla showing the quadrangular space; AN emerges posterior to brachial plexus and enters the QS divided in anterior and posterior ramus. D. Scanning starts viewing the brachial plexus at the axillary level, observing the fascia of the teres major muscle. E. Moving proximally the transducer (towards the axillary fossa) shows the teres major muscle fascia deepening and the subscapular muscle tendon; the QS is seen. F. with 180° arm extension, the teres major muscle closes the QS. G and H. the axillary nerve is observed above the subscapular muscle as a hyperechoic image next to the circumflex humeral artery.
With the arm positioned parallel to the thoracic wall with internal rotation and forearm pronated on the abdomen, a US probe is placed below and parallel to the clavicula identifying the coracoid process and lesser tubercle and intertubercular (bicipital) groove; then the arm is externally rotated, pushing the subscapular muscle rostrally and identifiable under the deep lamina of the deltoid fascia; the first portion of the AN is present between the deep lamina of the deltoid fascia and the superficial lamina of the subscapular muscle, where needle tip is placed. Interfacial position is confirmed after injection of 2 mL of normal saline, then 10 mL of 0.25% bupivacaine is injected. Rotating caudally the medial side of the probe and abducting the limb permits to directly visualize the AN and posterior circumflex humeral artery.
The injection is distributed on the anterior surface of the subscapular muscle and around the proximal insertion of the coracobrachialis and biceps brachial muscles. The sensory block is detected in AN area and areas supplied by the branches of the musculocutaneous nerve, lateral pectoral nerve, lateral supraclavicular nerve, and intercostobrachial nerve.
A complete AN blockade could provide anesthesia to the anteroinferior and lateral edges, and to part of the posterior aspect. of the shoulder joint capsule. The remaining shoulder joint areas are innervated by the SSN, which must be blocked if complete anesthesia of the shoulder is to be achieved. The LPN, or its articular branches, can be blocked by PECS I block or at the space between the coracoid process and clavicle (Figure 12) [41, 42].
US-guided anterior approach to AN blockade. A. Axillary nerve and its relations to subscapular, deltoid, and pectoralis muscles, axillary and circumflex humeral arteries, coracoid process, and humerus bone. B. Sagittal oblique ultrasound anatomy of the anterior axilla. C. Ultrasound scan: Transducer between coracoid process (medial) and the lesser tubercle of the humerus. Arm adducted and internal rotation. D. Transducer parallel to the inferior border of the clavicle, ultrasound mark is lateral. E and F. arm rotated externally/no abduction; subscapular muscle appears over humeral head. G and H. full external rotation and abduction of the arm. The medial side of the transducer is rotated inferiorly to obtain a sagittal oblique view of the axilla. The subscapular muscle is pushed rostrally and is identifiable under the deep lamina of the deltoid fascia. The cephalic vein is seen in the groove between deltoid and pectoralis major muscles. The axillary artery appears in the image and laterally to it, the axillary nerve is located. The needle shows the injection around the axillary nerve, on the surface of the subscapular muscle.
Clavicle fractures account for 2.6–4% of fractures in adults and 35% of shoulder injuries. The annual incidence is estimated between 29 and 64 per 100,000, and are distributed as follows: diaphysis 69-82%, lateral end 21-28%, and medial end 2-3%. There is often caudal displacement of the lateral fragment under the shoulder weight and elevation of the medial fragment by traction by the SCM. Infrequently, posterior displacement of the medial end can cause compression of the mediastinum and main vessels requiring urgent intervention. Non-displaced fractures are managed without surgery, while surgical management is preferred in cases of displaced fractures in active adults [43].
Innervation of the skin above the second rib is supplied by the supraclavicular nerves of the SCP. Terminal branches of suprascapular, subclavian, lateral pectoral, and long thoracic nerves pass through the plane between the clavipectoral fascia and the clavicle and, theoretically, contribute to collarbone innervation.
Common approaches in anesthesia for clavicle fracture surgery are GA, regional anesthesia techniques such as ISBP block combined with SCP block. The clavipectoral fascial plane (CPB) block (Figure 13) is accomplished by injecting 10 to 15 mL of LA deep to the clavipectoral fascia on the medial and lateral side of the fracture site. A SCP or supraclavicular nerves block should be implemented to provide a sensory block of the skin of the shoulder. This nerve block can potentially involve the PN if the injection is not performed accurately in the proper subcutaneous plane and using low volumes. The block can be used for diaphysis and lateral end interventions, but as isolated block for surgical anesthesia, it only works for diaphysis fractures (Figure 13) [44].
The peri clavicular fascial plane or clavipectoral planes block (CPB). A: Scan throughout all clavicle surface, identifying the fracture site (proximal segment is displaced upward) B: Initiate the US scan in a sagittal paramedian position C: Tilting the ultrasound probe, is positioned on the upper surface of the clavicle D: Identify the anterior and posterior borders of clavicle E: 25 G needle tip positioned between bony surface and periosteum (if seen: By the fractured site, the periosteum is usually detached F: After 1-2 ml injected, the periosteum is further disengaged G: A second hyperechoic line appears, which correspond to clavipectoral fascia H: Needle tip positioned in the gap between periosteum and clavipectoral fascia I: Initial injection under clavipectoral fascia. Track Injectate spread in caudal and cephalic way along the anterior surface of clavicle I: Alternatively, Clavipectoral fascia scanning and needle in plane insertion from caudal to cephalic over clavipectoral fascia between pectoral major and minor muscles; this plane is the target for injection of local anesthetic.
For lateral fractures, including acromioclavicular and coracoacromial ligaments, articular branch of lateral pectoral nerve should be blocked. Likewise, if the surgery involves the acromioclavicular joint, the SSN should be blocked. Yamak Altinpulluk states that in the description of Ince et al., the LA was injected between the periosteum of the clavicle and the surrounding fascia (assumed as the clavipectoral fascia), but cadaveric dissections show that the spread is between the clavicle and fascia of the pectoralis major muscle in the upper and anterior aspect of the clavicle, with anesthetic spread under the deep layer of superficial cervical fascia and the superficial layer of pectoralis major fascia. The naming of this block as CPB is misleading and suggests that this block should be named as peri clavicular block (PB) [45]. The publication of a series of cases by Kukreja et al., shows the injection of the LA between the clavipectoral fascia and the pectoralis major muscle, resolving the previous objections described by Yamak Altinpulluk et al. [46].
ISBP block targets the roots and trunks of the BP in the interscalene groove between ASM and MSM, and is directed towards C5-C6 nerve roots or UT. With higher volumes, C7 and even C8 nerve roots may be blocked. The block provides analgesia and anesthesia to the shoulder, lateral two-thirds of the clavicle, proximal humerus, and shoulder joint surgeries. Continuous infusion of 0.15% bupivacaine or ropivacaine (vs GA or intravenous anesthesia) provides adequate pain relief, similar side effects, and high patient satisfaction. ISBP block is associated with a high risk of PN blockade and HDP. Persistent PN palsy after ISBP block has recently gained wider recognition (reported incidence of 1:2000). Phrenic nerve palsy could be due to direct needle trauma or intraneural injection during landmark guided ISB but this complication has not been described with USG ISBP block. More peripheral BP nerve blockades are alternatives in scenarios in which avoiding PN palsy is critical, without clinically meaningful analgesic differences compared with ISBP block, except during recovery room stay [47]. Vocal hoarseness and Horner’s syndrome are due to self-limiting temporary blockade of the ipsilateral recurrent laryngeal nerve and stellate ganglion [48]. ISBP block cannot reliably block the C8 and T1 ventral rami [48, 49].
ISBP Blockade relies on the visualization of the relevant anatomy, needle-tip position and LA spread using USG plus peripheral nerve stimulation with or without injection pressure monitoring. USG allows fewer needle passes, lower volumes of LA, and better postoperative analgesia [1].
Figure 14 shows the scan process of interscalene space: At cricoid cartilage level, with transverse scan, identify the carotid artery and move the transducer laterally to locate the sonographic image of C5 and C6 TP; C5-C6 nerve roots are seen between the anterior and posterior tubercles and are traced in the groove between ASM and MSM, deep to the prevertebral fascia. The SCM lies superficially, and the PN runs medially over the ASM, away from the C5 root. Below the C6 TP and nerve root, C7 TP appears and the C7 nerve root can be seen anteriorly as hypoechoic round structure, lateral to vertebral vessels (identified by doppler color scan); meanwhile C5 and C6 nerve trunk are merging to conform to the UT; inferiorly to C7 transverse process, C7 nerve root conforms the MT. The dorsal scapular nerve (DSN) arises from the C5 nerve root and is imaged as a hyperechoic structure traversing the MSM, accompanied by LTN. Both must be avoided not needling through MSM. The block is performed positioning the tip deep to the C6 nerve root or UT and seeking the spread of LA anterior and posterior to the nerves, within the interscalene groove, and then repositioning of the needle superficial to the C5 nerve root or UT to obtain a satisfactory spread of LA. Do not needle between C5 and C6. 10-15 mL of LA (ropivacaine 0.75%) produce surgical anesthesia. Supraclavicular nerves blockade is added aimed to provide complete anesthesia to the shoulder cap.
Interscalene brachial plexus block.
The PN diverges at a rate of 0.3 mm per cm below the cricoid cartilage. Its blockade is reported in as 100% with a traditional landmark-based approach using volumes greater than 20 mL, and between 25 and 50% with lower volumes. Forced expiratory volume in 1 s (FEV1) may be reduced by up to 40%, and patients with comorbidities (obesity and respiratory disease) may develop troublesome dyspnea. ISBP block has been associated with an incidence of temporary neurological dysfunction in up to 14% at 10 days. Hypotension and bradycardic events occur in up to 20% during shoulder surgery, typically in the sitting position, and at around 30 min after the placement of an ISBP block. High circulating catecholamine concentrations and an underfilled, hyper contractile ventricle (induced by venous pooling) stimulates intramyocardial mechanoreceptors resulting in an abrupt reduction in sympathetic tone together with increased vagal tone. Prompt treatment with an antimuscarinic (ideally atropine) with or without sympathomimetic drugs is indicated [1].
Selective trunk block (SeTB) targets injection around individual trunks, with small volumes of LA. Produces anesthesia of the entire upper extremity (C5-T1) except the ICBN innervated area (T2). Is performed as one injection targeting UT and MT at interscalene and another one targeting LT at the corner pocket of the supraclavicular fossa (Up to 25 ml of LA are used). Produces HDP similar to UT approach [49, 50].
Shoulder surgery is accompanied by severe acute postoperative pain that continues to be an unresolved problem. The gold standard for analgesia after this surgery is the ISBP. Unfortunately, this block is associated with a high incidence of ipsilateral phrenic nerve block and the consequent HDP, which restricts its use in patients with pre-existing pulmonary involvement, so it is prudent to consider the practical options to avoid or reduce the incidence of this complication. Nerve block techniques without diaphragmatic involvement such as supraclavicular blocks, upper trunk blocks, anterior suprascapular nerve blocks, costoclavicular blocks, and combined infraclavicular-suprascapular blocks are some of the possible alternatives. It has been suggested that costoclavicular blocks could provide postoperative analgesia similar to ISBP along with a 0% incidence of HDP. It is not clear whether costoclavicular blocks could achieve surgical anesthesia for shoulder surgery. The anterior suprascapular nerve blocks have been shown to provide surgical anesthesia and analgesia similar to ISBP. However, the risk of HDP has not been adequately quantified. Of the remaining nerve blocks that preserve diaphragm function, supraclavicular blocks (with injection of posterolateral local anesthetic to the brachial plexus), upper trunk blocks, and combined anterior and infraclavicular suprascapular blocks achieve analgesia similar to ISBP, along with an incidence of HDP <10% [17, 25, 51].
Orthopedic surgeries are well known to be very painful. General anesthesia or regional anesthesia, or a combination of both, are optimal options for shoulder surgery. Regional nerve blocks are essential for postoperative analgesia and can be used alone or as a complement to GA, therefore the postoperative analgesia could be prolonged for 24 hours or more [49]. Regional anesthesia in the setting of GA has a relative contraindication but, with the use of USG, this statement has been challenged [52].
ISBP blockade is the most common approach and a highly effective technique, but with a high incidence of HDP, that contraindicates it in patients with lung disease or contralateral PN paralysis [25, 51]. Supraclavicular blocks vs. ISBP, result in similar pain control and patient satisfaction, but with an incidence of HDP exceeding 60%, when LA is injected intracluster, vs. 9% depositing LA posterolateral to neural cluster (in this setting, cluster refers to the confluence of trunks and divisions of BP) [25, 28].
UT block targets C5-C6 nerve fibers traveling with SSN and AN, producing analgesia not inferior to ISBP block and a 75% incidence reduction of PN involvement [21, 22, 23, 24]. The HDP occurs with an incidence of 5% [25].
AN block (posterior access) plus SSN block (sub supraspinous muscle access) produces a good analgesic effect in minor surgeries, compared to ISBP block, but spares the AN anterior articular branches, the lateral pectoral nerve articular branch, and subscapular nerve [25, 41, 45] and is inferior in terms of analgesia when compared to ISB in major surgeries. SSN block at sub omohyoid level extends to the UT almost always and occasionally to the middle trunk, with almost no PN block [33, 34, 35, 37]. It provides surgical anesthesia and similar analgesia to ISB [25]. It remains necessary to formally quantify the incidence of HDP. Both blocks should be accompanied by a supraclavicular nerve block at the lateral edge of the SCM to give analgesia to the skin over the shoulder and its contribution to the acromioclavicular joint [29].
AN block may be performed at the axillary fossa, producing anesthesia/analgesia that includes the anterior and posterior branches, with the advantage that intercostobrachial nerve block may be performed with the same puncture [38]. Access to the AN by anterior route is easy to perform and has the possibility of extending to the musculocutaneous nerve, superior subscapular nerve, lateral pectoral nerve and through the clavipectoral fascia, to the lateral supraclavicular nerve [41]. Clavipectoral fascia and peri clavicular block can provide anesthesia and analgesia for fractures of the middle third of the clavicle, without PN paralysis [44, 45, 46].
To date, the strategy that achieves analgesic equivalence with ISB with a 0%-incidence of HDP is the costoclavicular block. In 2019, Aliste et al. [53] compared ISB and costoclavicular block in 44 patients undergoing arthroscopic surgery, finding equivalent analgesia in both groups. Moreover, there is no evidence that this block results in surgical anesthesia [25]. Supraclavicular blocks (with LA injection posterolateral to the BP), UT blocks, and combined infraclavicular-anterior suprascapular blocks have been shown to achieve similar analgesia to ISB [54], coupled with an HDP incidence <10%. Decreasing LA injectate volume could avoid HDP altogether and should also be investigated for the provision of surgical anesthesia [25].
The anesthetic challenge imposed by shoulder surgery is considerable. This chapter reviews current options for regional anesthesia in this type of surgery. A regional technique, GA, or a combination of both can be appropriately used. Performing nerve blocks distally to the ISBP approach, PN paralysis can be reduced considerably, although not eliminated, taking care when performing them in patients with lung disease or contralateral HDP.
We thank MF Rojas for Figure 2. The authors also thank Dr. Victor Whizar-Lugo for his valuable support with this chapter.
The authors declare that they have no conflicts of interest.
axillary nerve anterior scalene muscle brachial plexus clavipectoral plane block dorsal scapular nerve general analgesia great auricular nerve hemi diaphragmatic paresis intercostobrachial nerve interscalene brachial plexus intravenous analgesia Local anesthetic Long head biceps tendon lateral pectoral nerve lateral suprascapular articular branch Levator scapulae muscle lower trunk long thoracic nerve medial brachial cutaneous nerve medial pectoral nerve medial suprascapular articular Branch middle scalene muscle middle trunk peri clavicular block phrenic nerve Quadrangular space sternocleidomastoid muscle superficial cervical plexus suprascapular nerve Selective trunk block transverse process ultrasound ultrasound guidance ultrasound image upper trunk
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Thus proteomics, an area of research that detects all protein forms expressed in an organism, including splice isoforms and post-translational modifications, is more suitable than genomics for a comprehensive understanding of the biochemical processes that govern life. The most common proteomics applications are currently in the clinical field for the identification, in a variety of biological matrices, of biomarkers for diagnosis and therapeutic intervention of disorders. From the comparison of proteomic profiles of control and disease or different physiological states, which may emerge, changes in protein expression can provide new insights into the roles played by some proteins in human pathologies. Understanding how proteins function and interact with each other is another goal of proteomics that makes this approach even more intriguing. Specialized technology and expertise are required to assess the proteome of any biological sample. Currently, proteomics relies mainly on mass spectrometry (MS) combined with electrophoretic (1 or 2-DE-MS) and/or chromatographic techniques (LC-MS/MS). MS is an excellent tool that has gained popularity in proteomics because of its ability to gather a complex body of information such as cataloging protein expression, identifying protein modification sites, and defining protein interactions. 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